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empreinte. 

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cas:  le  symbole  -^  signifie  "A  SUIVRE",  le 
symboie  V  signifie  "FIN  ". 

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et  de  haut  en  bas,  en  prenant  le  nombre 
d'images  nicessaire.  Les  diagrammes  suivants 
illustrent  la  m^thode. 


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Id 


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32X 


1 

2 

3 

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2 

3 

4 

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OUTLINES 


Modern  Chemistry, 


oi?.<3-^isrio. 


BASED  IN  PART  UPON  RICHES'  MANUEL  de  CHIMIE, 


Cj  ^^  ^,  C;  GILBER T  'wheeler, 

.^S^  ^  Professor  of  Chemistry  ,„  <hc  f.iiversity  of  Chicago. 


A.  S.  BARNES  &  00., 
New  York  and  Chicago, 

1S77. 


(?N 


11 


jktun    ii»iilH*»aM«|IIHh1*MMift— BW>t—fc» 


OTHER  WORKS  «y  PROF.  WHEELER. 


^■^n.nTj\iiv\TIVE  MINERALOGY.    A  pracllcal  guide  to  til 
"■"Tmu  oJ mSl  BpecleB,  cb.cliy  by  pl» H.cal  charactcr.B.ic«, 


A  practical  guide  to  the  recosul- 
uBical  characmriBiicB. 
tiou  ol  miuerui  i!n<;v,™=,  ^^■—■j  -^  .^-•i       $1.00. 

J..T,  .i    TiisTORr  CHARTS.    Five  in  mimher,  one  each  of  the  fol- 

lowing:   '^l*""*"-'*'     p,"   '  _    1,,  ,,11   ovurTtK)  lliietralioui).  Wholly 

MiNKKAi.8,  Rooks  a"'l/°*?'^^,,,V  «-  no     The  Bet 830.00. 

hand  colored    pace  of  cac'.v  chart,  S'.OO-    ^"'■8'-' 

NATURAL  HISTORY  PRIMER.    A  conciso  dcBcriptlve  work  .m /.<>oi.- 

oov  and  MiNEBAi-ooY.    Price  


IN   PREPARATION. 
THE  CIIEMIriTRY  OF  BUILDING  MATERIALS. 


-\ 


C  O  P  Y  R  I  G  II  T 

G.   GILBEllT   WHEELER. 

1877. 


R. 


PREFACE. 


recogni- 

...8100. 
)f  tho  fol- 

KIIIIATKS; 

1,  Wholly 
...830.00. 

;  jn  7,(ioi.- 

....gioo. 

important 
rmHii  and 
MiiBunmH 
....82.00. 


'S^ 


Organic  chemistry  has  not  as  A'et  secured  in  Ameri- 
can colleges  sufficiently  lu-oiiounced  attention  to  create 
a  demand  for  text-books  of  considerable  size  or  ex- 
tended scope.  In  these  simple  Outlines,  therefore,  no 
more  has  been  attempted  than  this  circumstance  would 
appear  to  warrant.  It  is  hoped  that  the  necessary 
conciseness  in  method  and  form  of  expression  has  n(»^t 
resulted  in  any  important  sacrifice  of  i^erspicuity  in 
thought  or  arrangement. 

It  would  have  been  easier  to  prepare  a  larger  work. 
From  the  bewildering  wealth  of  results  aliorded  by  the 
labors  of  investigators  in  this  branch  of  science,  tlie  aj)- 
propriate  selection  of  that  suited  to  the  wants  of  stu- 
dents was  by  no  means  an  easy  task. 

It  is  assumed  in  these  Outlines  that  those  entering 
niwn  the  study  of  Organic  Chemistry  have  previously 
made  themselves  acquainted  with  Inorganic  Chemistry 
as  taught  by  some  modern  author,  such  as  Miller  or 
Barker,  or  have  at  least  become  familiar  with  the  gen- 
eral principles  of  modern  chemical  philosophy.  The 
author  taking  this  for  gnuited,  has  not,  therefore,  en- 
cumbered the  work  with  a  restatement  of  that  which 
appertains  to  the  theory  of  chemistry  in  general. 

In  addition  to  the  organic  portion  of  Riche's  Man- 
uel de  Chimie,  a  translation  of  which  by  the  author 


]'KKKAOK. 


lias  seiTCtl  ill  part  as  basis  for  tlioso  Outlines,  tlie 
works  of  Miller,  Fuwiies,  Williaiuson,  Itoseoe,  aii<l 
others  have  heeii  tVcely  used,  while  the  cheMiical 
journals  of  Kiirope  and  Anieri(!a,  including  their  latest 
iiuuibers,  have  heon  consulted  and  the  data  whicli 
they  afforded  utilized. 

For  the  henetit  of  any  who  may  cai'e  to  read  the  full 
original  papers  from  which  are  taken  the  abridfjjed  ex- 
cerpta  of  recent  articles  there  arc  gi\in  references, 
within  parentheses,  to  a  list  of  authorities  to  i»e  found 
in  the  author's  work  on  Medical  Chemistry. 

Lest  any  regard  the  numlie)"  of  characteristic  re- 
actions of  the  more  important  compounds  as  insufH- 
cient,  it  should  be  stated,  that  it  was  not  within 
the  plan  of  the  author  to  adapt  this  work  to  the 
recpiirements  of  an  analytical  manual.  Not  more 
than  two  or  three  analytical  tests  are  therefore  given 
as  a  rule,  and  even  this  number  only  in  the  case  of  the 
leading  compounds.  A  similar  exj)lanation  might  be 
proifered  to  any  who  may  miss  the  full  technical  de- 
tails relative  to  certain  compounds  which  are  usually 
given  in  works  on  applied,  or  technological  chemistry. 

Throughout  the  work,  the  centigrade  thermometer 
and  the  metric  system  of  weights  aiul  measures  are 
employed,  unless  otherwise  ispecitically  stated. 

C  (iir.UEKT  Wiii;i;i.i;u. 

Univeusity  ok  CiiiCACio,  October,  1877. 


CONTENTS. 


iNTRonirrTORT,       -  _  _ 

Cl.ASSrFICATIOX  OF   OuiJANK)   CoMI'DUNDS, 

HoMOLouoi^s  Skhiks, 
Hydrocaruons,     -  . 

Alcohols, 

"  MONATOMIC, 

"        Diatomic, 

"        Triatomic, 
Ethers, 

Aldkhyds,  -  _  _ 

Acids,  -  ^  _ 

"  MoNATOMir, 

"        Polyatomic,   - 
Alkaloids  or  Ijases, 

"        Artificial, 

"        Natural, 
Neutral  Fatty  Bodies, 
Sugars, 
Glucosides, 

VegETAHLE  CirEMISTRY, 

Cellulose,  - 

Starch,  » 

Dextrik,        -  „  _ 

Gums,     -  -  .  ._ 


PAQK 

7 
10 
12 
18 
44 
46 
68 
64 
69 
85 
90 
06 
112 

-  127 
i;}2,  170 

-  137 
174 

-  181 
193 
199 
205 

-  210 
214 

-  216 


ORGANIC  CHEMISTRY. 


INTRODUCTORY. 

Organic  chemistry  is  the  science  of  the  compounds 
of  carbon. 

Only  a  small  number  of  otlier  elements  are  met 
with  in  natural  organic  substances;  they  are  hydrogen, 
oxygen  and  nitrogen,  sometimes  also,  sulphur,  phos- 
phorus, and  very  rarely  certain  other  elements. 

Chemists  liave  succeeded  in  incorjjorating  most  of 
the  elemental  substances  in  organic  bodies,  yet  the 
larger  number  even  of  the  artificial  compounds  include 
only  tiie  four  elements  first  named. 

Paraftine  is  found  by  analysis  to  contain  only  carbon 
and  hydrogen,  and  is  therefore  called  a  hydrogen- 
carbide.  The  hydrocarbides  are  compounds  so  stable 
and  fundamental  that  some  chemists,  as  Schorlemmer 
for  instance,  have  even  defined  organic  chemistry  as 
"the  chemistry  of  hydrocarbons  and  their  derivatives." 

From  alcohol,  or  sugar,  we  may  obtain  carbon  and 
water.  These  bodies  thei-efore  are  composed  of  three 
elements:  carbon,  hydrogon  and  oxygen,  and  are  called 
carhohydrates ;  though  by  some  chemists,  this 
term  is  restricted  to  those  compouvids  containing  car- 


«^iiiiift-iiiiiiT«i 


8 


OKOANIO     OHKMISTKY. 


1)011  with  hydrogen,  and  oxygen  in  snt-li  i)ropoi-tions  as 
would  form  water. 

If  albumen  is  decomposed  by  heat,  the  result  is  not 
only  carbon  and  water,  but  also  ammonia ;  this  sub- 
stance accordingly  is  nitrogenous. 

The  number  of  organic  bodies  is  very  great.  As  they 
are  composed  of  a  small  number  of  elements  only,  it 
may  be  concluded  that  the  latter  unite  in  a  very  great 
variety  of  proportions  ;  it  is  therefore  of  much  impor-  ' 
tance  to  know  the  molecular  grouping  of  these  ele-^ 
ments.  The  mere  fact  that  the  kind  and  number  ot 
elements  entering  into  a  compound  are  known,  is  not 
sufficient  proof  that  its  molecular  structure  is  really 
determined.  Synthesis  niust  often  be  employed  to 
coutirm  the  results  of  analysis. 

Berthelot  has  specially  occupied  himself  with  the 
synthesis  of  organic  bodies,  and  has  artificially  produced 
a  great  number  of  them.  Other  chemists  have 
experimented  in  the  same  direction  during  the  last  15 
or  20  years.  However,  Gerhardt's  opinion  advanced 
in  ISSi;  vi/.,  "  The  vital  force  ah)ne  operates  by  syn- 
thesis  and  reconstructs  the  edifice  demolished  by 
chemical  affinity,"  has  ceased  to  be  held  as  true. 


t.■,■,■^i^ 


iso:meris]m. 

Carbon,  hvdrogen,  oxygen  and  nitrogen  are  not  only 
capable  of  uniting  in  a  great  variety  of  proportions, 
but  these  elements  also  furnish  nmnerous  isomenG 
bodies  ;  these  comprise  substances  which,  while  com- 


' 


_L 


jortions  as 

isult  is  not 
tins  sub- 

;.    As  tliey 
its  only,  it 

very  groat 
ncli  inipor-  ' 

these  ele- 
number  of 
own,  is  not 
■e  is  really 
nployed  to 

If  with  the 
ly  produced 
mists  have 
the  last  15 
m  advanced 
ates  by  syn- 
nolished  by 
.  true. 


are  not  only 
proportions, 
)us  isomeric 
I,  while  coni- 


ISOMERISM. 


9 


posed  of  the  same  elements,  have  different  properties. 
Sometimes  the  physical  properties  alone  are  different; 
we  tlien  Ixawe physical  isomerism. 

Wlien  the  chemical  properties  themselves  are  modi- 
fied, this  is  denominated  chemical  isomerism.  Of  the 
latter,  two  kinds  are  recognized. 

I.  Polyvierism;  cyanogen  and  paracyanogen  are 
examples  of  this  variety  of  isomerism ;  the  latter  is  to 
be  considered  as  cyanogen,  CN  condensed,  thus 
(CN)n ;  it  is  a  polymeride  of  cyanogen.  The  weight  of 
the  molecule  of  these  two  substances  is  therefore  dif- 
ferent. 

II.  Metamerism.  At  other  times  the  isomerism 
results  from  a  different  grouping  of  elements  in  tlie 
compound,  the  molecular  weiglit  remaining  the  same. 

We  will  illustrate  this  by  tv/o  examples  : 
a)  Methyl  acetate, 
and  b)  Ethyl  formiate. 

Acetic  acid  =  H-O-C2H3O. 

Methyl  hydrate,  or  methyl  alcohol=H.O-CII,. 

When  these  two  bodies  react  they  furnish  water  and 
methyl  acetate,  Clls-O-CJIgO^-CsrisO.,. 

Formic  acid=II-0-CIK). 

Ethyl  hydrate,  or  ethyl  alcohoWlI-O-CJI,.     ' 

JS'ow  formic  acid  contains  CHg  less  than  acetic  acid, 
and  hydrate  of  ethyl  contains  one  molecule  of  CII2 
more  than  does  hydrate  of  methyl.  As  these  substan- 
ces in  reacting  lose  one  molecule  of  water,  it  is  there- 
fore clear  thac  the  compound  obtained  will  have,  like 
the  preceding  cue,  the  formula  CjlIoO,.     But  these 


10 


ORGANIC    CHEMISTRY. 


! 


two  products  are  not  identical  substances,  for  the  lor- 
iner  treated  with  alkalies  regains  the  molecule  ot  water 
which  it  had  lost,  reforming  acetic  acid  and  methyl  hy- 
drate, while  .he  latter  regenerates  formic  acid  and  ethyl 

hydrate. 

These  bodies  accordingly  differ  m  the  arrangement     , 

of  their  molecule;  they  are  called  metamenc  bodies. 
Finally  there  exist  bodies  which  are  isomeric, prop- 
erly so-called,  possessing  the  same  formula,  having  the 
sanie  general  reactions,  the  same  chemical  functions, 
and  which  differ  only  in  a  very  few,  chiefly  physical, 
properties  :  such  are  oil  of  turpentine  and  oil  ot  lemon, 
each  having  the  formula  Cmll,  g. 

CLASSIFICATION    OF    ORGANIC    COM- 
POUNDS. 
CuKMicAL  TYPKS.-The  idea  of  referring  organic  bod- 
ies to  some  simple  viodel,  or  type,  was  originally  work- 
edout  by  Laurent  and  Gerhardt,  1846-53,  though  the 
eenns  of  their  ideas  on  classification  are  to  be  tound  in 
the  earlier  papers  of  the  distinguished  _  American 
chemist  T.  Sterry  Hunt.       {Am.  Jour.  Set.  [2]  xxxi. ) 
The  four  principal  types  are  : 

I.  The  hydrogen  type,  jj,  Jorllj. 

II.  The  oxide  or  water  type,  jj'  |  O' '  orlljO. 

ii;  )    ^^^ 

III.  The  nitride  or  ammonia  type,ll'^  ^  N"  '  or  11 3  N. 


L 


MtlWaHBfttlWJlHIIUlliJMHilltM 


ORGANIC     TYPES. 


11 


,  for  the  for- 
;ule  of  water 
i  methyl  hy- 
cid  and  ethyl 

arrangement 
nerlc  bodies, 
mn'io,  prop- 
Si,  havhig  the 
isl  functions, 
efly  physical, 
oil  of  lemon. 


IC    COM- 

rorsranic  b:>d- 
iginally  work- 
3,  though  the 
to  be  found  in 
ed  American 
Sci.  [2]  xxxi.) 


'  orlljO. 


.N"'orlI,N. 


IV.    The  marsh  gas  type  fj ,'  >>  C'v  or  H^C. 

H'J 

Of  tlie  leading  groups  of  orgjinic  bodies,  we  refer  to 
the  hydrogen  type:  hydrocarbides,  aldehvds  and  the 
compounds  of  metals  and  metalloids  vvitii  organic 
radicals. 

To  the  water  type  are  referred  the  alcohols,  ethers, 
men-iiptans  and  aidiydrides. 

To  the  ammonia  type  belong  the  amides,  amines, 
and  alkalamides,  all  of  which  are  denominated  com- 
pound  ammonias. 

Marsh-gas  is  the  type  to  which  carbon  dioxide  is 
referred,  as  well  as  some  of  the  more  comjDlex  or^ano- 
metallic  bodies. 

Further  details  as  to  the  relation  of  each  of  these 
classes  of  compounds  to  their  respective  types  will  be 
gwf^n  as  each  particular  class  is  studied. 

Besides  the  simple  type,  Kekule  has  proposed  com- 
pound  types  formed  by  the  combination  of  two  of  the 
four  types  already  given.  Thus  the  typos  of  ammonia 
and  water  coirbined  serve  as  a  pattern  for  carbamic 
and  oxamic  acids: 


N"' 


Carbanilc  acid. 

H 


H 

CO" 


N 


OxamIc  Acid. 


iifo 


H 


■IWMMMWXMMMIX'Xkl 


1 


12 


I      ! 


ORGANIC     ClIKMISTRY. 


HOMOLOGOUS   SKKIKS. 


The  members  of  a  series  of  compounds  winch  have 
the  connnon  difference  of  C  lU  are  said  to  he  hornolo- 
gnus.     Two  or  more  such  homologous  series  are  termed 

uologous. 

The  first  idea  of  progressive  senes  in  organic 
chemistry  was  enunciated  by  James  Schiol,  ot  bt. 
Louis,  Mo.,  in  1842.  It  was  afterwards  ^dopted  by 
Gerhardt  unchan-ed,  save  only  in  name.     (lOO-o-l  Jo.) 

Tlie  subjoined  table  will  illustrate  the  nature  of  these 
series  Each  vertical  column  forms  a  homologous 
.cries  in  which  the  terms  differ  by  CII,,  and  each  hori- 
zontal line  an  isologous  series  in  which  the  successive 
terms  differ  by  IIj.  The  bodies  of  these  last  series  are 
designated  as  the  monocarbon,  dicarbon  group,  etc. 

C  H4    C  Ha 

CoH„    C„H,    CoHg 

cJh^    C:,H„    C3H,    C,H, 

C,H,„C,Hs    C,He    C^H^C.H, 

CH     C,H,oC,H«    C.H«C,,H,C,H 

C„H,,  C„H,,  C„H,„  C„Hs  CeH„  C„H,  C«H., 

The  terms  of  the  same  homologous  series  resemble 
one  another  in  many  respects,  exhibiting  similar  trans- 
formations m.der  the  action  of  given  re-i.gcnts,  and  a 
regular  gradation  of  properties  from  the  lowest  to  tlie 
liio-he-st ;  thus,  of  the  hydro-carbons,  C„ll,nvi.  "le  low- 
est terms  CII,  Cdl,,  and  Calls,  are  gaseous  at  ordinary 
temperatures,  the  highest  containing  20  or  more  car- 


HOMOLOGOUS     SERIE.i. 


13 


liicli  have 
e  homolo- 
ire  termed 

1    organic 
el,  of    St. 
lo]ited  by 
100-5-195.) 
re  of  these 
oniologons 
1  each  hori- 
successive 
it  series  are 
3up,  etc. 


C«H, 

i%  vcsenible 
miUir  trans- 
gents,  and  a 
owcrit  to  the 
in.2.  the  low- 
^  at  ordinary 
)r  more  car- 


bon-iitouis,  are  solid,  while  the  intermediate  com- 
pounds are  liquids,  becoming  more  and  more  viscid  and 
less  volatile,  as  they  contain  a  greater  number  of  car- 
bon-atoms, and  exhibiting  a  constant  rise  of  about  20" 
C.  (36°  F.)  in  their  boiling  points  for  each  addition  of 
Clfa  to  the  molecide. 

The  individual  series  are  given  in  the  following  ta- 
ble, with  the  names  ])roposed  for  them  by  A.  \Y. 
Hoffmann:  ' 


E  thine 
CJI, 

Propine  Propone 

C3H4  Cgll, 

Quartine  Quartone  Qiuwtune 

C4n„  C4H4       c^ii, 

Quintine  Quintoue   Quintune 

C„Hs  QHe           C,H4 

Sextine  Sextone      Sextune 

CeHio  Cells           C„H„ 


The  foi-mul8B  in  the  precedin.L  tables  represent  hydro- 
carbons all  of  which  are  capable  of  existing  in  the 
separate  state,  and  numy  of  winch  have  been  actually 
obtained.  They  are  all  derived  from  saturated  mole- 
cules, C„Il2n.2,  by  abstraction  of  one  or  more  pairs  of 
hydrogen-atoms. 

But  a  saturated  hydrocarbon,  CII4,  for  example,  may 


Methane 

Afethene 

cir4 

CHj 

Ethane 

Ethene 

CJIe 

0,\l, 

Propane 

Propene 

C3IIB 

Callo 

Quartano 

Qiuirtene 

C4ll,0 

C4II8 

Quintane 

Quintene 

CslLa 

C,H,o 

Sextane 

Sextene 

CoIIu 

Coll,, 

14 


ORGANIC    CHEMISTRY. 


dve  up  1,  2.  3,  or  any  number  of  hydrogen-atoms  m 
exchan-e  iw  other  elements;  thus  marsh  gas,  CH4. 
subiccted  to  the  action  of  chlorine  under  various  cir- 
cumstances, yields  the  substitution-products. 


CH3CI,  CHC,C1^  CHCI3 


CCI4, 


which  may  be  regarded  as  compounds  of  chlorine  with 
the  radicles, 

(CII3)',       (CII.)",       (Ctts)'",       C'v; 

and  in  like  manner  each  hydrocarbon  of  the  series, 
C„ll2„«,  may  yield  a  series  of  radicles  of  the  forms, 

(C„IIw)',(CnH.n)",    (C3.U-1)'"     (CnH.n-.r,&C. 

each  of  which  has  an  equivalent  value,  or  combining 
power,  corresponding  with  the  number  of  hydi-ogen- 
atoms  abstracted  from  the  original  hydrocarbon.  Those 
of  even  equivalence  contain  even  numbers  of  hydro- 
gen-atoms,  and  are  identical  in  composition  with  those 
in  the  table  above  given  ;  but  those  of  uneven  equiva- 
lence contain  odd  numbers  of  hydrogen-atoms,  and 
are  incapable  of  existing  in  the  separate  state,  except, 
uerhaps,  as  double  molecules. 

These  hydrocarbon  radicles  of  uneven  equivalence 
are  designated  by  Hoffmann,  with  names  endmg  in  yl, 
those  of  the  univalent  radicles  being  formed  trom 
methane,  ethane,  &c.,  by  changing  the  termination 


i-\ 


^. 


8 


HOMOLOGOUS     SERIES. 


15 


-atoms  in 
gas,  CH4. 
irious  cir- 


CCI4, 
orine  with 


the  series, 
e  forms, 

combining 
'  hydrogen- 
•bon.  Those 
•8  of  hyflro- 
1  with  those 
;ven  equiva- 
-atoms,  and 
tate,  except, 

equivalence 
mding  in  yl. 
bnued  from 

termination 


<zne  into  yl ;  those  of  the  trivalent  i-adicles  by  chang- 
ing tlie  final  e  in  the  names  of  the  hivalent  radicles, 
methene,  etc.,  into  yl/  and  similarly  for  the  rest.  The 
names  of  the  whole  series  will  theretore  be  as  follows  : 


Jkletliane 

CJI„ 
Ethane 
C3H8 
Propane 
&c. 


(CH3)' 
Metliyl 
(C,H,)' 
Ethyl 
(C3H:)' 
Propyl 


tfec. 


(CH,)" 
Methene 

(C,n4)" 

Ethene 

(CsHr.)" 

Propene 


(CII)'" 
Methenyl 
(CJI3)'" 
Ethenyl 
iC,Uj' ' ' 
Propenyl 


Fi-om  these  hydrocarbon  radicles,  others  of  the 
same  degree  of  e(iiiivalence  may  be  derived  by  partial 
or  total  replacement  of  the  hydrogen  by  other  elements, 
or  compound  radicles.  Thus  from  propyl,  C3H,,  may 
be  derived  th€  following  univalent  radicles:— 


,    C3WI     ,      ^      0311,01, 
Lliloi'opropyl       Tetrachloi-opropyl 

Cgll.ClsO  CsHoCCK)' 

Trichloroxypropyl  Cyanopropyl. 

C3ll,(NH,)0  (■'3H„(CIl') 

Amidoxypropyl  Methylpropyl 


Oxypropyl 

C3He(N6.,) 

Nitroprojjyl 

Diethylpropyl. 


From  the  radicles  above  mentioned,  all  well-defined 
organic  compounds  may  be  supposed  to  be  formed  by 
combination  and  substitution,  each  radicle  entering 
into  combination,  just  like  an  elementary  bodv  of  the 
same  degree  of  equivalence. 


— -i!-T 


16  ORGANIC    CHEMISTRY. 

TABLE  TO  ILLUSTSATE  THE  ARRANGEMENT  OK  THE  MORE 


SericB. 


General 
Formula. 


Types . 


llydro- 
carbouB. 


Sulphides. 


CnlUn 


CnTT2«+i  I  o 
VnVzH+i )^ 


1.  C    Ua 

2.  C2  n4 

3.  CjHg 

4.  C4  Hg 

5.  Cs  IIio 


6.     Cf,  Ilia 


7.    C7  U14 


8.    Cg  ni6 


9.    C9  IIiS 
10.    C10H20 


Hi 

ni- 


ce Il3)2S 
(C3Us)2H 


(Csnn)23 


Hi  , 


Chlorides  or 
Haloid    Ktliers. 


CnH2H  +  iCl 

C  113  CI 
C2H5  CI 
C,ai7  CI 
C4H9  CI 
C5H11CI 


Alcohols. 


CnH2n+ 1 )  n 

U        r 


CSH17CI 


Hf 


CI  U3  HO 
C2H5  UO 
C3H7  HO 
C4H0  HO 
CsUiiHO 
CfiHisHO 

CSU17HO 


Hi" 


1 ^ 


THE  MORE 


Alcohols. 


:nH2n+i  If, 

U        r 


C.  U3  HO 
C2H5  110 
C3H7  HO 
C4iIo  HO 
CsUiiIlO 

C6H13HO 


ORGANIC    COMPOUxVDS.  If 

IMPORTANT  ORGANIC  COMPOUNDS  IN  HOAU.I.OOOUS  SERIES. 


Mercaptans, 


CnJUn+i I u 
H  f« 


Aldehyds. 


CnlX2n-i  O  I 
U  1 


Acids. 


C»Il2«-lO  I 


Simple  Ethers.     Compound  Ethers, 


C  H3  US 
C2IIS  US 

C4H0  US 
CsUiiHS 


Cninn+i     , 


c  H  o,n 


"C    H     O.    I      (CU3).0  CH3C    n     O2      ,. 


C2  H3  o,n 

C3  Hs  0,H 

C4  H7  0,H     HC4  117  O2 


HC21130.       (C2ns)20    I  c.iis  021x30.    ... 

^'^^^^O^  I     C2H5C3U5O2      3. 

C'^Hj  C4  117  Oi      4. 


lies  H9  02  (Csllp)20  C5II..CSH9O2      s. 


18 


OUOANIC    CItKMlSTia. 

CAEBIDES    OF    IIYDEOGEN. 


J';,  /.y5™o»A;,  ».Kl  their  ,.ro,«n-,    l-l.)--' 
drogeu,  or  II'  ^ 


ir  I 

IF  r 


FIRST  SEEIES. 


General  Formula,  CuH2n-s- 
ACETYLENK,  OU   mnVUKUOKN    DICABmDE. 
BUcovered  by  Davy  and  cou^position  determined  by  Hertbelct. 
£S^Sy.0.92.    Density.  13.    Molecular  .ei^bt,  26. 

i;^....    o^^^^^^'o-  Of  Carhon    arul  Jlydrogen 
U;  to  cou,nvratively  recent  tuue.  ^^^^^^^ 
.laeL  impossible  to  unite  ^^^^X 
rectly.     Berthelot,  however,  succeeded  in  aom« 

■"pr^l-.-T..eapp«t„..„ic.hUee,„p,o,ea 


^— ^ 


CARBIDES    OF    HYDKOOEK. 


19 


inds,  al?o 
physical 

IS  BtU'.lu'"! 

)ssess  but 
)ide8  are: 
,il  of  tnr. 
»etroleuiu, 

six  series, 
ule  of  hy- 


[DE. 

1  bi  IJertlielct. 

•  weight,  26. 

Hydrogen. 
iiti  been  Cviu- 
lydrogeu  di- 
doiug  tUib  in 

he  employed 


in  tliis  remarkable  synthesis,  consisted  of  a  ^'lass  Hask, 
provided  with  two  lateral  tiilmluros  through  which 
l)asscd  two  metallic  rods,  terminating  in  carbon  ])oints, 
an<l  which  a]>proached  so  as  to  form,  when  connected 
witii  a  powerful  battery,  an  electric  arc.  The  corks 
through  which  these  rods  passed  were  provided  with 
another  opening  each,  to  wliich  a  tul>e  was  adapted. 
Through  one  of  these  tubes  hydrogen  was  admitted 
and  through  the  other  the  products  of  the  reaction 
passed  as  they  were  formed. 

The  gas  was  collected  in  a  solution  of  cuprous 
chloride  in  ammonia.  A  red-precipitate,  acetylide  of 
copper  was  formed,  which  was  thrown  upon  a  filter  and 
treated  with  hydrochloric  acid  in  a  flask,  whereuju.n 
acetylene  was  set  free. 

Many  oi-ganie  comjwunds  produce  acetylene  -n 
subjecting  their  vapors  to  the  action  of  electric  dis- 
charges. 

Acetylene  is  also  produced,  as  a  rule,  whenever  or- 
gam'c  matter  is  decomposed  by  heat. 

Propebties.— Acetylene  is  a  colorless  gas,  having  a 
disagreealjle  odor.  It  is  moderately  soluble  in  wat'er, 
and  has  not  been  liquified.  It  is  decomposed,  at  about 
the  temperature  at  which  glass  melts,  into  carbon, 
iiydrogen,  ethylene,  ethyl  hydride  and  condensed 
hydrocarbides,  among  Avhich  Berthelot  has  found  ben- 
zol. Thenard  lias  recently  obtained  it  both  as  a  liquid 
and  a  vitreous  solid.     (9 — 78 — 219.) 

Acetylene  burns  with  a  faliginous  flame.  It  de- 
tonates violently  and  witho;it  residue  wlien  mixed  with 


ORGANIC     CHEMISTRY. 

2  5  volumes  of  oxygen.     Cuprous  acetylide  is  an  ex- 
plosive body.     It  is  sometimes  formed  in  brass  gas- 
pipes,  and  lias  been  the  c^  aise  of  fatal  accidents. 
^  Chlorine  acts  upon  acetylene  with  f  f  ^^  ^^^'-f^'; 
there  is  often  detonation  accompanied  by  l.glit      O 
.noderating    the  action  the  compound  C,II,C1,  can 
he  obtained,   which,  as  well  as   the  body  (  ,I1.U,, 
can  also  be  prepared  by  the  action  of  antimonic  chlo- 

ride  up(m  acetylene.  ,.   ,    • 

As   acetylene  is  not  imcommonly  studied   m  con- 

nection  with  inorganic  compounds,  a  more  detailed  ac 

count  of  this  hvdrocarbide  need  not  be  given  here.  _ 
Acetvlene  is"  the  prototype  of  a  homologous  seraes 

of  hyd^ocarbides,  of  which  the  general  tormula  is, 

The  following  members  of  this  series  are  known: 

AUylene,     -        -        "        '    ^'  ^* 

Crotonylene,  -        -        "        y^*  "« 
Valerylene,         "        '        '     p    S' 

Rutylene,  -        -        -        p'-S'" 
Beuzylene,         -       -       "    ^ib^^^s- 


I 


ETHYLENE. 


21 


is  an  ex- 
rass  gus- 
ts. 

B  energy; 
^ht.  On 
LCI 2  can 

onic  clilo- 

[1   in  con- 
etailecl  ac- 
[i  here, 
fous  series 
lula  is, 


!  known: 

4 
0 

A 

t8 
•28' 


SECOXD  SERIES. 

General  formula,  C^Hju. 

ETHYLENK. 

Bynonyma:  Elayl,  Olcflant  gas. 

Formulii  Co  II.j 

8p.  Gr.  0.97.    Molecular  weight,  28. 

This  gas,  for  no  good  reason  other  than  custom,  is 
always  t^tudied  in  inorganic  clieniistry,  usually  in  con- 
nection  with  the  consideration  of  illuminating  gas,  of 
which,  with  methane,  it  forms  a  prominent  constit- 
uent. 

Ethylene  is  the  type  of  a  class  of  homologous  hydro- 
carbides,  of  which  the  general  formula  is: 

Each  member  of  the  series  is  related  to  an  alcohol 
from  which  it  may  be  obtained  on  treatment  with 
bodies  having  a  great  affinity  for  water,  as  sulphuric 
acid  or  zinc  chloride. 

C„IL,._,,  +  0,-ILO  =  CJL„. 


i   i 


ill 


!  ill 


••'  ••*  i'l 


2-2 


ORGANIC     CHKMISTKY. 


We  note  -he  following  members  of  tins  series  : 

.       -        -    G,  H, 

C;,     Hf, 

-    C4  Hs 

,       -       -       G,  Hio 


Ethylene,  -        -        - 
Propylene,      -        -        - 
Butylene,   - 

Amylene,        -        -        " 
Hexylene, 

Heptylene, 

Octylene,    - 

Nonylene,       -        -        " 

Paramylene, 

Cetene,  -        -        "        " 

Duodecylenc,      - 

Tridecylene,  (Paraffin?)* 

Tetradecylene, 


Cg  H12 

C  T    11  1  4 

G,,n,, 


*A.  G.  Pouchet(60-[3]  4-868)  has  prepared  f-m  P^-mn  by 
oxydalion  with  nitric  acid,  paraffin  ac.d,  C-MlUiO-i.  fiom  whicU 
he  deduces  CsmHm  as  the  formula  for  paraffin. 


<>.Vj. |j-jx.-'."'i 


series  : 

6 
^8 
[lO 
[,2 

Itc 

Its 
^2  0 

im  paraflln,  by 
^,  from  which 


MKTHANE. 


2a 


THIRD  SEEIES. 

GenciMl  formula,  Cn  Hin+a* 
MKTII^VNE. 

Discovered  by  Volta  iu  I'.TS. 

Synonyms;  Metliyl  hydride,  Marsh  gas,  Formenc. 

Formula  CHi or  CH3.H. 

Sp.  Or.  0.559.    Molecular  weight,  16. 

Permanent  gas,  not  liquiflable,  neutral. 

Not  discussed  in  detail  here  for  tlie  same  reasons  as 
given  under  Ethylene. 

Methane  is  the  first  member  of  the  following  veiy 
important  liomolog(nis  series: 

C  If,         methyi  hydride,  or  methiuie. 


C^  li« 

ethvl 

>( 

"  ethiuu'. 

C3IIH 

l)ropyl 

t( 

"  propane. 

C4  11,0 

butyl 

(( 

"  butane. 

CsII,. 

amyl 

(( 

"  amane. 

c„ii„ 

hexvl 

a 

"  hexano. 

C,II,„ 

lieptyl 

a 

"  he[)tane. 

f  8  11,8 

octvl 

a 

"  octane. 

C„II,o 

nomyl 

t( 

"  nonane. 

f  ioll« 

decyl 

t( 

"  decane. 

Cnll,, 

undecvl 

k( 

"  undecane 

C12II06 

bidecvl 

u 

"  bidecane. 

.im\i^»tu*» 


5r*' 


24 


OKGANIC    fllKMISTKY. 


Cjsir.a  tridecyl      '• 

C,4n:jo  tetradecyl  " 

C,,,ir;H  pentadecyl" 

Ciellsj  liexadecyl  " 


"  tridecane. 
"  tetradeciine. 
"  pentadecane. 
"  hexadeciuie. 


Nearly  all  the  members  of  this  series  have  been 
found  ill  American  petroleum,  mixed  with  members 
of  the  preceding,  or  ethylene,  series. 

Crude  petndeum,  refined  by  fractional  distillation, 
is  still  a  mixture  of  various  hydrocarbons. 

The  commercial  names  given  to  the  products  sep- 
arated at  the  different  boiling  points,  do  not  appertidn 
to  chemical  compounds,  or  bodies  having  a  definite 
composition. 

Subjoined  is  a  table  based  on  Dr.  C.  F.  Chandler's 
Report  on  Petroleum,  (100 — '7'2-41)  showing  the 

PRODUCTS  OF  THE  DISTILLATION  OF  CKUDK  PETUOLEUM.* 


H 

O  H 

a  . 

fc" 

h  > 

■A  H 

KAKB. 

—  3 

CUIEr  USES. 

a  a 

s.  » 

=  i^ 

U  r- 

1 

Cymogune 

OOC. 

1  liencrally   uncoudoused  — used    In 
1     Ic.u  niachliies. 

.025 

18.3 

\  Coiidoiiced  by  Ice  and  salt— used  as 
■(     an  uniL'Bthetlc. 

(iftsolenc 

15^ 

i 

.««5 
VOfi 

48.8 
8S.S 

Used  In  mnkInK  "nlryHH." 
(Used  for  oll-clotliB,  cleuntiig.  ndul- 

(;  NiiplilhH 

U  Nitphllin 

'■10 

.;S4 

101. -1 

■<     terntlng  kerosene,  etc.  For  piilnts 

A  Nuplitlm 

1 

.~M 

148.  H 

(     and  varnifhcH, 

Kciixinu 

4 

Used  to  adiillerate  kerosene  oil. 

Kcroneno  oil 

or. 

,80» 

ITfi.U 

Ordinary  oil  for  lumps. 

MliH'rnI  i<i)oriii  . . 

.MIT 

aiH.H 

I.nl)iieutin|{  oil 

.8:)3 

SOl.U 

liiihr'catin';  machinery. 

Piinillln 

in'i 

Siillil. 

Miimif/iciiire  oC  cundlea. 

♦Ui-  nrranged  from  Dr.  C.  V.  Chandler's  Report  on  Petroleum,  presented  to 
the  Uoard  of  Hoallh,  of  the  City  of  New  York,  18;0. 


lie. 

ine. 

le. 

ive  been 

members 

itilliitioii, 

nets  sop- 
ijipertidii 
1,  definite 

liandler's 
tbe 

;OLKUM.* 


id  — used    lu 
salt— used  as 

iuiiing,  iidiil- 
a.  Fur  piiiiits 

osenu  oil. 


prosuntud  to 


METHANE. 


35 


UNSAFK    KKRtBKNE. 

Many  accidents  occur  hy  ex])losion  of  lamps,  wlien 
kerosene  oil  contains  too  much  ot'tlie  lighter  oils,  ben- 
zine and  naphtha.  This  makes  the  oil  too  readily  in- 
tlaiiunable.  fbr  the  lighter  oils  are  di-iven  out  by  heat- 
ing (as  when  a  lamp  or  kerosene  stove  is  bnrning\and 
theii-  vapors  mixed  M-ith  the  oxygen  of  the  air  fbrin  a 
dangerous  explosive  mixture.  There  is  a  law  le.juir- 
ing  mamifacturers  to  keep  kerosene  f)il  free  from  these 
lighter  oils,  unfortunately  not  always  faithfully  en- 
forced. 

The  temperature  at  which  kerosene,  on  heating  in 
an  open  vessel,  emits  vapors  which  readily  catch^fire 
on  approaching  a  burning  body,  is  called, 'technically, 
the  "flash  point,  'and  that  at  which  the  kerosene  itself 
inflames  is  called  the  'burning  point." 

FOSSIL  EKSIN8.  AXD  Blir jrKN. 

These  substances  include  amber,  retinasphalt,  as- 
phalt, retinite,  and  many  otherallied  bodies  which  are 
chiefly  contained  in  the  tertiary  strata.  In  many  in- 
stances they  are  the  pnjducts  of  the  action  of  an  ele- 
vated temperature  upon  vegetable  bodies;  and  when 
this  is  the  case,  they  form  irregular  deposits  which  im- 
pregnate tlie  strata  around.  In  many  cases  the  bitn- 
inens  occur  in  regidar  beds,  which  appear  to  have  been 
formed  in  a  manner  similar  to  the  deposits  of  true  coal. 

Certain  important  building  stones  have  been  found 
to  be  more  or  less  iini)regnated  with  bitumen. 

Such  is  the  limestone  obtained  at  the  artesian  well 


J 


i 


26 


ORGANIC    CHEMISTRY. 


(luivrry  in  tlie  city  of  Chicago,  and  the  celebrated 
BuL'iia  Vista,  i;Ohio,)  sandstone  used  extensively  in 
Cincinnati;  also  employed  at  Chicago  in  various 
prominent  public  buildings,  as  the  post-office  and 
Chamber  of  Commerce.  The  author,  in  making  a 
chemical  examination  of  the  latter  stone  for  the 
United  States  Trea>nry  Dqiurtment,  fo  .ud  it  to  con- 
tain '2^^  jier  cent,  bituniinous  matter. 


lelebrated 
sively  in 
various 
ffico  and 
)iaking  a 
}  I'oi-  the 
it  to  cou- 


BKNZOL. 


27 


FOURTH  SERIES. 
Ganeral  Ibriuiila  C„  Hon^H,. 

BKNZOL. 

Synonyms;  BenzL-ne,  Benzine. 

Formula  C« Ho- 

Sp.  Gr.  0.88.    Molecular  weight,  78. 

8p.  Gr  of  vapor  2.70. 

Density"     "         39. 

Solid  at  4°.    Boils  at  80.5° 

Benzol  is  obtained,  witli  acetylene  and  etl.vlene,  in 
tl.e  decomposition   ot    organic    t^ubstances   bv   beat 
and   Its  production  is   especially   favored  wlR-n    the 
temperat'ire  is  kept  at  a  high  i,oint  for  some  time 

JUiiyleno  and    methane  form    at    a   tolerably  low 
tempenitnre.     Acetylene,  which  is  richer  in  carbon 
IS  produced   at  a  higher   temperature.     IUvaoX   and 
especially  napthalin,  being  still    more  cirboimceous, 
are  tornied  at  an  extremely  high  temperature. 

Lerthelot  lias  i)repared  l)en;col  syntlieticallv  by  con- 
ducting  mothaue  tribromid.,  QllWv,,  ovei-  red-hot 
coi)j)er: 

6(CriBr,)+9CH  -C„II,,+9CuBr.,      - 

o  fr'n.  T^'  ''''  ^""^'^''^••«^  *i«  condensed  acetylene: 


I 


28 


ORGANIC     CHEMISTRY 


boils  at  110= 
"  "  139° 
"      "  165= 


Oric,nnally,  benzol  was  prepared  by  a  pro:.-ess  analo- 
gous to  that  which  fiiriii8he.s  methane,  i.  e.,  by  distill- 
ing benzoic  aeiil  with  lime, 

C,n«02+CaO  ==  Ca  C  Oj+CoHo. 

At  present  it  is  obtained  in  immense  quantities  from 
the  tar  which  is  formed  as  an  accessory  product  in  the 
manufacture  of  illuminating  gas. 

At  the  high  temperature  of  the  gas-retort  other  pro- 
ducts, homologous  with  benzine,  are  formed  as  well; 

Toluene  C^  Hg 

Xylene  tl,,  H,„ 

Cuniene  C„   Hia 

Cymeue  Cm  Hi  4 

and  other  hvdrocarbides,  as  napthalin  C.oHs,  autlira- 
cene,  also  various  sulphur  compounds,  notably  carnoii 
bisulphide;  several  oxygenated  compounds,  as  phenol 
C„II,f),  cresylol  C^IIsO ;  nitrogenous  compounds, 
as    aniline    C,H,N,    and    various   members  ut    its 

homologous  series.  ,       .  ,  -a 

Benzol  is  a  colorless,  neutral  licpiid,  with  a  specific 
gravity  of  0.89,  almost  insoluble  in  water  but  soluble 
in  alcohol  and  ether. 

It  dissolves  sulph.ir,  phosphorus,  lodme,  the  ditter- 
ent  resins,  and  fatty  substances;  this  latter  property 
causes  it  to  be  employed  similarly  with  con.mercial 
"benzine"  for  cleansing  purposes.  Care  must  be  ta,ven 
to  rub  with  a  piece  of  cloth  having  an  open  texture, 


r 


I' III 

-Jnj 


BENZOL. 


29 


3  analo- 
j  distill- 


ties  from 
jt  in  the 

ther  pm- 
as  well; 


,  autlira- 
\\'  carlioii 
\%  phenol 
inpoiincls, 
ii'S  «->t'    its 

a  specific 
ut  soluble 

the  differ- 
■  jiroperty 
onimercial 
st  be  talven 
lu  texture, 


that  it  may  remove  tlie  benzol  by  absorption,  witliout 
whicli  the  spot  would  reappear  after  evaporation  ot  the 
solvent. 

Benzol  burns  with  a  fuliginous  flame.  Nascent 
oxy-en  gives  with  it  various  products,  and  notably 
oxalic  acid  and  carbon  dioxide. 

Chlorine  and  l)romine  yield  crystalline  compounds 
with  benzol.  Benzol  is  the  simplest  member  of  a 
group  of  bodies  known  as  tlie  aromatic  oompoumls,  of 
which  we  shall  proceed  to  describe  some  of  the  more 
important. 

For  distinguishing  benzol  from  the  benzine  of  com- 
merce, which  is  made  from  petroleum,  Brandberg 
recommends  to  place  a  small  piece  of  pitdi  in  a  te.-S 
tube,  and  pour  over  it  some  of  the  substance  to  be  ex- 
amined. Benzol  will  immediately  dissolve  the  jntch 
to  a  tar-like  mass,  while  benzine  will  scarcelv  be  col- 
ored. 

NiTROBEXZOLCJIgXOs. 


ing 


This  body  is  obtained  by  treating  benzol  with  fum 
nitric  acid. 

CJI«+IIXOa==  C6n,(N-0a)+II/). 

Nitro-benzol  is  a  yellowish  oil,  crystallizing  at  37°, 
has  a  sweet  taste  and  an  odor  which  lias  led  to  its  use 
in  perfumery  under  the  name  of  essence  of  mirbane. 
Taken  internally  it  acts  as  a  poison. 

On  treatment  of  nitro-benzol  with  nascent  hydrogen, 
hydrogen  sulphide,  or  other  reducing  agent,  we  oblaiil 


f" 


80 


ORGANIC    CHEMISTRY, 


aniltne,  which  is  a  colorless  liquid,  boiling  at  182°. 
It  does  not  act  upon  litmus,  jet  combines  with  the 
acids,  tbnning  crystalliziible  compounds. 

Aniline  gives  with  chlorine,  bromine  and  nitric  acid 
products  of  substitution  which  are  very  numerous  and 
well  defined.  It  reacts  upon  the  iodides  of  niothyl, 
ethyl,  etc.,  forming  the  corresponding  amines,  or  bodies 
constrveted  on  the  type  of  ammonixi,  having  one  or 
more  of  the  hi/drogen,  atoms  replaced  hy  an  organic 
compound  radicle: 


Aniline 
Methylaniline 
Ethyl  methylan  iline 


Cell.N 


N-^II 


C,II,X 


(  CJI5 
X  ■  C  Ila 
III 

CsIIisX  --=  N    C  II, 

C.2I15 


CbIIb  or,  when  free,  (€6115)2 ,  is  the  radicle  phenyl, 
hence  aniline  is  properly  phenylamine. 

Aniline  has,  during  the  last  score  of  years,  acquired 
great  importance,  as,  under  the  influence  of  oxydizing 
bodies,  it  forms  most  remarkable  tinctorial  com- 
pounds. 

If  a  small  quantity  of  aniline  is  added  to  a  solution 
of  chloride  of  lime,  the  liquid  is  coWred  violet,  which 
color  disappears  in  a  few  moments.  In  1858,  Perkins 
obtained,  by  the  action  of  potassium  bichromate  and 
sulphuric  acid,  a  beautiful  purple,  which  is  known  in 


Kiria 


t  182°. 
ith  the 

ric  acid 
>us  and 
iiothyl, 
*  bodies 
'  one  or 
>rganie 


II5 
II. 


JI5 


phenyl, 

icqiiired 
:ydizing 
,1  corn- 
solution 
t,  which 
Perkins 
late  and 
mown  in 


bp:nzol. 


;il 


commerce  as  7n,nive.  Shortly  after,  Yergnin  obtained 
a  iiijignilicent  red  coloring  matter  on  heating  aniline 
with  tin  dichloride. 

This  substance,  known  under  the  names  of  aniline- 
red,  fuchsin,  magenta,  etc.,  is  now  very  economi- 
cally obtained  with  arsenic  oxide  in  place  of  the  tin 
dichloride,  which  is  reduced  to  arseuous  oxide  by  the 
reaction. 

iroffmann  has  shown  that  aniline-red  is  .a  salt  of  a 
colorless  base,  which  he  calls  rosaniline;  this  substance 
has  the  formula  0^11^,-^,0,  or  C*ir,,,N3,II,0. 

In  the  past  few  years  there  have  been  produced 
green,  yellow  and  black  cohjrs,  all  originating  from 
aniline.  These  substances  dissolve  in  alcohol,  and  dye 
wool  and  silk  without  in  any  way  weakening  the  fabric. 
They  have  a  magnificent  lustre,  but  their  permanency 
is  not  of  the  highest  grade. 

The  consumption  of  aniline  for  dyeing  has  now  come 
to  something  enormous,  amounting  in  Germany  alone 
to  over  15,000  tons  per  annum. 

^  The  aniline  colors  are  employed  in  injecting  tissues 
for  microscopic  preparations. 

For  a  fuller  account  of  the  aniline  colors,  a  larger 
work  should  be  consulted. 

The  history  of  aniline  affords  one  of  the  most  re- 
markable instances  of  the  value  of  scientific  chemical 
reseai-ch,  when  perseveringly  and  skillfully  applied, 
for  at  first  few  substances  seemed  to  promise  less; 
and  the  gigantic  manufacturing  industry  at  present 
connected  with  this  compound,  in  its  applications  as  ;-. 


1 


i^" 


32 


OKOANIC     '  HEMI.STKV, 


tinctorial  agent,  offers  a  singular  contra^st  to  the  early 
ex])eriinents  upon  this  hotly,  when  a  lew  ounces  t'ur- 
nisht'tl  a  supply  which  exceeded  the  most  sanguine  ex- 
pectations of  tlie  early  discoverer.-:  of  this  hody. 

Phionol,  CellsO. 
Synonyms:  Hydrate-of  phenyl,  carbolic  acid  or  phenic  acid- 
It  occurs  in  castoreum,  though  usually  procured  iVoni 
the  portions  of  coal-tar  distilling  over  between  170" 
and  105'.  They  are  agitated  with  caustic  sodr., 
water  added  to  separate  the  insoluble  oils,  and  the 
phenol  dissolved  in  the  alkali  is  liberated  as  a  crys- 
talline mass,  on  decomposing  the  potassium  compound 
with  hydrochloric  acid. 

Salicvlic  acid,  distilled  with  an  excess  of  lime,  also 
furnishes  phenol; 

dneOa  +  CaO  =  CaCO»  +  C^HfiO. 

Ifphenyl-sulphuricacid,^''^^''  j- SO,,  obtained  by  di- 
rect action  of  sulphuric  acid  upoi'.  phenol,  is  heated 
with  potassium  hydrate  to  about  300%  potassic  ])henol 
CJIjKO  is  obtained.  Phenol  is  therefore  ol)tained 
from  benzol  under  the  same  conditions  as  alcoiiol  is 
obtained  from  ethylene,  the  corresponding  hydro- 
carbide. 

Piienol  crystallizes  in  handsome  needles,  fusible  at 
34=  and  boiling  at  IbS".     It  -s  little  soluble  in  water. 


.m 


lie  early 
loes  t'lir- 
'iiiiie  ex- 


ile acid- 
red  tVoiii 
leii  170- 
:ic  >>»)<l!;, 
and  the 
IS  .a  crys- 
»m]X)Uiid 

iirie,  <also 


d  by  di- 

s  heated 
ic  ])henol 
obtained 
Icoliol  is 
r  hydro- 
fusible  at 
ill  water, 


( 


PHKNOL. 


33 


very  soluble  in  uloliol  and  ether.  I'Iumk.I  furnishes 
M-itli  chlorine,  bromine  uud  iodine  numerous  substitu- 
tion ])r()ducts. 

Phenol  lias  come,  like  alcohol,  to  have  a  generic 
sigiiitication,  there  being  a  number  of  analogous  coin- 
I):>inids,  though  only  this,  the  ordinary  i)henol,  is  an 
iniiiortant  body.  Heated  with  concentrated  nitric 
acid,  it  furnishes  yellow,  very  bitter,  crystals  of  the 
body  known  as 

PicKic  or  CAienAz<JTii;  acid. 

Picric  acid  is  also  formed  when  silk,  benzoin,  aloes, 
indigo,  etc.,  are  treated  with  nitric  acid. 

This  acid  is  very  largely  used  in  dyeing,  either  di- 
rectly to  produce  a  yellow  color,  or,  combined  with  in- 
digo, to  ])i*oduce  a  green. 

Phenol,  though  called  carbolic  acid,  does  not  decom- 
pose the  carbonates,  or  combine  with  the  metals  to 
form  true  salts.  Phenol  dissolves  in  sulj)liuric  acid 
without  coloration,  if  pure,  and  forms  i)lienyl-sulpliuric 
acid  or  sulpho-carbolic  acid 

MilJ.i  )  en 
XI  )^^^' 

which  gives  definite  salts  with  the  metals.     One  of 
these,  the  ])henyi-8ulpliate  or  sulpho-carbolate  of  so- 
dium XadJIftSOj,  is  claimed  to  have  valuable  ]iroper- 
ties  as  a  ]>ro|)liy lactic  against  scarlet  fever. 
Phenol  gives  certain  reactions  of  the  alcohols  ;    this 


>a&*p   JjrfirSf  N  B 


L 


i   ! 


34 


ORGANIC    CHKMISTUY. 


somewhat  oxiilains  the  origin  of  tlie  name  given  it  by 
Berthi'liit,  This  body  is  the  type  of  a  class  of  coui- 
pounds  which  contains: 

Cresylol  obtained  from  creosote  C-,  H-,  O 

Phlon-lol       "  "  "  CgllioO 

Thymol         •'         "       essence  of  thyme  CioHuO. 

I'lIYSIOI.OOICAL  ACTION  OF  I'HKXOL. 

Phenol  attacks  the  skin,  producing  a  white  stain. 
It  coagulates  albumen  and  is  employed  with  great 
success  as  an  antiseptic  and  disinfectant.  It  is  used 
externally  in  a  diluted  state  to  dress  wounds  which 
suppurate,  also  in  many  surgic:d  case^3. 

It  is  sometimes  used  internally.  Large  doses  of  it 
are  ]ioisonous.  Carbonate  and  es^pecially  sacchariite  of 
calcium  are  considered  as  antidotes  for  phenol.  Grace 
C'alvcrt  has  announced  that  olive  or  almond  oil  is  a 
still  better  antidote. 


OIL    OF    Tl'UI'KNTI^^E, 


35 


\'en  it  by 
3  of  com- 


ite  stain, 
itli  great 
t  is  used 
Js  which 

3ses  (if  it 
•Iiiinite  of 
1.  Grace 
i  oil  is  a 


FIFTH  SERIES. 

General  Formuli,,  Cn  Iha-i. 

K8SEXCK,     OB    OIL    OK    TUKI'KNTIXK. 

Formula  CioHm. 

Deiisitj'  of  vapor  compared  with  air  4.7. 

Molecular  weiglit,  130. 

Boils  at  160. 

Tm-pentine  is  extracted  from  sever.d  varieties  of  the 
family  of  oonifem,  notably  from  the  pine,  fir  and 
larch. 

Tlie  products  vary  somewhat  with  the  nature  of  the 
tree,  but  they  have  many  common  characteristics; 
their  composition  is  the  same,  tlieir  density  is  nearly 
identical  and  their  toiling  point  very  nearly  so.  Their 
rotary  action  on  the  solar  ray  varies  largely. 

Isomeric  carbides  are  found  in  other  families  of 
plants,  in  the  aumniiaoem  fninily  for  instance,  as  the 
lemons  and  oranges.  These  con'tain  carbides  verv  dif- 
ferent, as  evidenced  by  their  odors  and  other  phvsical 
properties,  also  different  in  certain  chemical  relations, 
yet  liaving  the  same  composition  as  oil  of  turpentine.' 
There  are  also  various  polymers  of  this  carbide. 

This  ejitire  series  of  hydrocarbons  can  be  divided 
into  three  groups.     The  tirst  contains  carbides  havinc^ 


'^4 


36 


OKGANIC     ClIKMISTUY. 


tlic  formula  C,„n,6,  tlieir  boiling  points  being  below 
200",  and  including  : 


Donsity. 

Boiling  at 

Oil  of  turpentine, 

0.8(5 

157"  to  160". 

(( 

cloves, 

0.92 

140"    "  145". 

u 

lemon, 

0,85 

170"    "  175". 

>( 

orange, 

0.83 

175"    "  180". 

u 

juniper, 

O.Si 

about  1 60". 

ki 

berganiot, 

0.85 

"      183". 

li 

pepper, 

O.SG 

"      167". 

u 

elemi, 

0.85 

'•      180". 

Tlie  carbides  of  the  second  group  have  the  formula 
C.J0II32,  their  boiling  is  above  200",  they  are  : 


Oil  of  copaiva,  0.91 

'•      cubebs,  0.93 


245". 
240". 


The  third  group  contains  the  non-volatile  carbides, 

such  as 

Density- 
Caoutchouc,     .         -         -         -         0.!'»3. 
Gutta-percha,  -         -         -     0.9S. 

The  rotary  power,  constant  for  eaeli,  varies  with  the 
difl'erent  species. 

French  oil  of  turpentine  causes  the  ])lane  of  polar- 
ization to  deviate  to  the  left;  the  American  variety 
turns  it  13°  to  the  right;  oil  of  lemon  causes  a  devia- 
tion of  50"  to  the  right;  in  the  case  of  essence  of 
elemi  the  deviation  amounts  to  lOO".     ISonie  of   the 


S99BI 


OIL    UK    TUKPENTI-VK. 


37 


eing  below 


ing  at 
o  160". 
"  14-5". 
"  175". 
"  ISO", 
It  1 60". 

183". 

167". 

ISO". 

the  formula 

e  : 

!45". 
>40". 

ile  carbides, 

Density 
0.!»2. 

0.98. 

'ies  with  the 

no  of  polar- 
•icaii  variety 
uses  a  devia- 
:'  essence  of 
ioine  of   the 


essential  oils  of  the  first  grouj>  contain  o.xvgc-n  coin- 
ponuds  as  well  as  the  carbi)hyd rides. 

The  principal  chemical  differences  between  the 
members  of  the  group  ai-o  the  facility  with  which  they 
are  oxydj^ed  and  their  reaction  with  hydrochloi-ic 
acid.  Essence  of  turpentine  becomes  resinous  rapidly 
when  exposed  to  the  air  and  finally  solidifies.  Es- 
sence of  lemon  becomes  viscid  after  a  considerable 
time.  Hydrochloric  acid  produces,  with  esscMice  of 
tur])entine,  aliipiid  and  a  solid  cmpound,  having  each 
the  same  composition,  C,oTi,«,  IICl,  which,  after  a 
few  M-eeks,  becomes  a  dichlorliydride,  (by  some  denomi- 
nated a  dichl(.rhydrate),  C„JI„„2Il('i.  Essence  of 
lemon  also  gives  two  UicliLrhyd rides  at  once,  one 
liquid,  the  other  solid. 

Oil  of  turpentine  may  be  obtained  in  a  pure  state, 
on  distilling  the  commercial  article  in  a  vacuum! 
Thus  obtained,  turpentine  is  colorless,  limpid,  very 
volatile,  and  has  a  characteristic  odor.  It  is  insoluble 
in  water;  very  soluble  in  alcohol  and  ether.  It  buruo 
with  a  snu)l<y  flame;  on  exposure  to  the  air  it  oxvdize. 
and  becomes  resinous.  The  same  effect  is  produced 
more  rapidly  with  oxide  of  lead  and  some  other  ox- 
ides which  render  the  oil  siccative  and  suitable  for  use 
in  painting.  J.  M.  Merrick  (100-4-289)  has  noticed 
the  circumstance,  imijortant  in  its  technical  ap]dica- 
tions,  that  oil  of  turpentine  attacks  metalic  lead  quite 
strongly;  tin,  on  the  other  hand,  not  at  all.  Turpen- 
tine, if  exi.osed  to  the  air,  mixed  with  a  solutio.i  of 
ludigo,  absorbs  oxyg.-n  and  transf^^rs  it  to  the  indigo. 


I---; 


38 


OKfiANIC     ClIKMISTRY. 


which  loses  its  color,  yielding  a  product  of  oxj'datiou 
called  isatin.  Under  these  circumstances,  the  turpen- 
tine does  not  change,  anil  a  given  quantity  of  the  es- 
sence can  absorb  se\  eral  huiulred  times  its  volume  of 
oxygen,  and  oxydize  an  indeiinite  quantity  of  indigo. 
This  oxygen  is  probably  the  active  modification,  or 
ozone.  Heated  to  3(M»°  in  a  hermetically  sealed  tube, 
it  cliangi;s  into  two  ])roducts,  t)ne,  isunieric,  called  iso- 
tKrpentine,  which  boils  at  177",  and  which  exerts  a 
rotatory  j)Ower  of  10°  to  15"  to  the  left;  the  other,  a 
polymer  called  meta-terehentheiu;,  Cj„11m  boiling  at 
360°. 

tmiKR  SKIUFS  OF  IIVDKiK'AUBinKS. 

Clnnamene  Calls  is  a  very  refracti\e  liquid  with 
a  density  of  O.J)24,  boiling  at  146".  Stijrol  which 
is  produced  from  stoi-ax  is  converted  at  205",  into  a 
polymeric  solid,  termed  2[eta-styrol  or  Draconyl.  If 
styrol  is  made  to  act  ujjon  acetylene,  or  ethylene,  at 
a  red  heat,  there  is  obtained  the  \qv\  important  hydro- 
carbide  naphtludin  C\i^lf^.  This  is  a  body  crystalliz- 
able  in  very  handsome  plates,  and  ii  ordinarily 
obtained  from  coal  tar  b}'  distillation  between  200° 
and  300";  heavy  oils  pass  over,  out  of  which  uapLtha- 
liu  crystallizes;  on  cooling,  the  mass  is  ])re?sed  and 
])urified  by  sublimation.  It  fuses  at  79°  and  distils  at 
220". 

Nai)lithalin  is  associated  in  coal  tar  with  a  hydro- 
carbide,  beautifully  crystallizing  in  K)ng  needles,  fus- 
ing at  03"  and  boiling  at  285".     This  is  acerujphtene 


— 


ALIZARIIV. 


31) 


)xvdatiou 
le  turpen- 
f  the  es- 
iolume  of 
)t'  indigo. 
:;ation,  or 
iileil  tube, 
jallotl  iso- 
exerts  a 
0  other,  a 
oiling  at 


^uid  with 
"ol  which 
5",  into  a 
(>7iyl.  If 
hylciic,  at 
lilt  hydro- 
cry!<talliz- 
ordinarily 
i^een  200'' 

napLtha- 
I'^sed  and 

distils  at 

a  liydro- 
jdlos,  fns- 
maphtene 


C,,II,n.  Another  l)ydn.c;ii-l)ide  isul.s,.  found  in  this  tar 
anthracene.  Its  formula  is  C„ll,o.  It  forms  very 
dn.iinutive  crystalline  ]»late8  fusing  at  210"  and  boil- 
ing at  3<;(i".     Its  vapor  is  extremely  ac,  id. 

This  body  has  recently  enabk..l  chemists  to  rej.ro- 
duce  the  coloring  jirinciple  of  ma.hler;  ^dharln 
<  nllsO,.  It  IS  obtained  on  oxydizing  ai-.thracene  by 
means  of  a  mixtnre  of  bichromate  of  potassium  and 
siilphuric  acid,  which  gives  oxijaiithrac, no  C,^II,().. 
Tins,  with  fused  potassa,  furnishes  a  combinafion  of 
potassium  and  alizarin,  from  which  the  latter  is  pre- 
cipitated  by  an  acid.  It  has  the  li.rm  of  brilliant 
bronze-colored  needles,  identical  with  natural  alizarin 
obtained  from  madder. 

Alizarin  sublimes  at  215 «  and  is  very  stable,  little 
soluble  in  cold  water,  but  readiiv  sniuble  in  boiJi,,.' 
water.  It  is  easily  dissolved  in  alcohol,  ether  and  car- 
bon bisulphide. 

Its  chemical  character,  not  ,piite  well  defined  as 
yet,  ap].ears  to  i.Iace  it  anumg  the  pheiu.Is.  (See 
page  H;].)  ^ 

The  artificial  production  of  alizarin  from  anthra- 
cene, thus  furnishing  a  cheap  substitute  for  madder 
Hec.,;,.t  dye-stuff  used  in  printing  calicoes,  is  one  of 
tie  latest  and  in..st  noteworthy  triumphs  of  oriranic 
ciiemistry.     Thousands  of  acres  of   la.ul  in  Europe 
especially  in  Alsafia,  noNV  <lcvote.l  to  the  culrure  of 
madder,  may  be  restored  to  cereal  or  other  food  a-n-i- 
ciilture.  '^ 


Before  leaving  the  hydrocarbons  proper,  it  shouM 


iO 


ORGANIC     CHEMISTUY. 


Ito  stated  that  CDiiipounds  of  caHiou  and  hydrogen  of 
extra-terrt'strial  origin  have  been  found  in  certain  met- 
eorites, l)y  J.  Lawrence  Smith.     (80-7<J-3SS.) 


CAMIMIOU. 


Caniphcjr  is  Ui^ually  considered  at  this  point,  on  ac- 
count of  its  intimate  relation  tothe  o.xydizedes^sontial 
oils  in  composition, and  to  turpentine  m  many  chemical 
reactions. 

Bertiielot  regards  camphor  as  an  aldeliyd.  Xekiilo 
phiees  it  among  tlio  ketones. 

Camplior  exists  in  various  parts  of  the  Znnrus 
camphora,.  To  obtain  it,  the  wood  is  finely  divided 
and  heated  with  water  in  a  metallic  vessel,  closed  by  a 
cover  tilled  with  straw.  The  cami)hor  is  condensed  in 
grayish  crystals  on  the  straw,  forming  tlie  crndo  cam- 
phor of  commerce ;  it  is  afterwards  sublimed  in  a  glass 
retort  as  a  further  pnrificatio.  . 

Camphor  is  a  ciystallizetl  body,  having  a  burning 
taste  and  au  aromatic  odor.  Its  density  is  0.90  at 
10".  It  is  elastic  and  with  difficulty  p\dverized,  which 
can,  liowever,  be  easily  eflfec ted  on  moistening  with  a 
few  drops  of  alcohol.  Water  dissolves  only  about  ^ih-^ 
l)artof  it;  thrown  ui)on  pure  water  it  floats  on  the 
surface  with  a  gyratory  motion.  It  is  siduble  in  alco- 
hol, ethi'r,  acetic  acid  and  essential  oils ;  it  is  sublimed 
at  ordinary  ten?]  loratu  res  where  kept  inclose  vessels, 
and  deposits  again  on  the  cooler  side  of  the  recep- 
tacle. 

It  burns  with  a  smoky  flame  and  oxydizes  on  being 


J, 


I'drogeii  of 
rtiiiii  luet- 


itit,  on  ac- 
dossontiiil 
y  cliemical 

1.     Kekulu 

'\y  divided 
jlosed  by  ii 
iidcnsed  in 
jrudo  cnm- 
l  in  ii  glass 

a  burning 
'  is  0.90  at 
izcd,  which 
ing  witli  a 
about  T-„V7 
tats  on  the 
l)le  in  alco- 
is  sublimed 
)se  vessels, 

the  rocep- 

es  on  being 


^\ 


Ti 


I 


RKSINS,  BALSAMS,  GUM-KESIxVS. 


41 


boik'd  with  nitric  acid,  yielding  camphoric  add 
<  'loUiA  which  isbibasic.  Heated  with  zinc  chloride  or 
anhydrous  phosphoric  acid,  it  fnrnislies  Cyuiol  C.oII,,. 

The  anthor  found  (1-146-73)  that  on  treatment  of 
can.phor  vith  hypochlorous  acid  he  obtained  the  new 
body,  C,olli3('10,  wliich  lie  denoininates  tiwnocldoi'- 
ra,nphor\  this,  on  treatment  with  alcoholic  potassium 
hydi-ate,  yiehled  oxycamplm'  C,oII„i(),.. 

('amj)hor  is  very  extensively  employed  in  medicine 
and  pharmacy. 

EK8IXS,   BALSAMS,   GUM-KKSINS. 

These  l)odies  are  products  of  th6  oxidation  of  essen- 
tial nr  volatileoils.  The  name  oi gum-renui  is  applied 
to  those  which  contain  a  gum,  and  halmtm  to  those 
which  contain  essential  oils  and  an  acid,  usuallv  cin- 
namic  or  benzoic,  in  addition  to  the  resin  which  is 
present  in  both.  A.  H.  Prescott,  the  eminent  au- 
thority on  proximate  analysis,  defines  balsams  as  "  natu- 
ral mixtures  of  volatileoils  with  their  oxidation  pro- 
ducts,—resins  and  solid  volatile  acids." 

They  are  snbstancos  more  or  less  colored,  hard  and 
brittle.  They  are  fusible,  non-volatile,  and  burn  with 
a  luhginons  flame.  They  are  insoluble  in  water,  gen- 
eraMy  soluble  in  alcohol,  ether  and  essential  oils. 

Several  of  them  are  acid.  This  is  the  case  with  the 
most  important  of  them,  as  theresinof  the  pine,  called 
colophony,  frrmi  which  three  isomeric  acids  have  been 
obtainod-thej>;?iiV,  sylvic,  and  plmario,  C^ll^O.. 


42 


ORGANIC    riI?:MISTRT. 


This  resin  constitutes  the  fixed  residue  obtained  on 
distilling  crude  turpentine.  It  is  used  for  in-eparing 
varnish,  in  soldering,  and  in  certain  combinations  witli 
the  alkalies,  called  resin-soaps. 

Subjoined  are  given  the  names  and  the  origin  of  the 
princijial  resins,  oleo-resins,  gum-resiiis  and  balsams. 
With  some,  the  position  assigned  them  in  this  classi- 
fication is  not  definitely  settled. 

RKSINS. 

Amber  is  found  in  the  lignites  and  in  the  alluvial 
sands  of  the  J>altie. 

Arnic'iu,  the  active  principle  of  Arnica  Eoot. 

Cannabiu,  the  active  principle  of  Indian  Hemp. 

Castorin,  a  seci-etion  of  the  Beaver  (Castor). 

Ergotin(f),  the  active  principle  of  Ergot  of  common 
rje. 

Mastic,  a  resinous  exudation  of  the  Mastic,  or  Lent- 
isk  tree. 

Burgundy  Pitch,  an  exudation  of  the  Spruce  Fii-, 
Abies  cvcelm. 

Pyrethrin,  the  active  principle  of  tlie  Pcllito'y  root. 

Eottlerin,  a  crystalline  resin  from  Kaniala,  the  min- 
ute glands  which  cover  the  capsules  of  liottlera  tinc- 
toria. 

OLKO-KKSINS. 

Copaiva,  a  resinous  juice  of  the  copaifera  officinalis 
found  in  Spanish  America. 

Wood-oil,  au  oleo-resin  from  the  Dipterocarpus 
turhiiuitns. 


"w't'jfti 


RESINS,  BALSAMS,  GUM-RESINS. 


43 


btained  on 

])rei)ariTig 

itions  with 


igin  of  the 
<1  balsams, 
this  classi- 


le  alluvial 

oot. 

I  Hemp. 

01'). 

if  common 

c,  or  Lent- 

^pruco  Fir, 

lito'y  root, 
a,  the  min- 
tle?'a  tinc- 


ojfic'inalls 
terocarpus 


Elemi,  an  exudation  of  an  nnkndwn  tree,  (probablv 
Cannar'nim  commune). 

Common  Frankincense,  a  concrete  turpentine  of  tlie 
P.' I) us  tmda. 

Canada  balsam,  the  turpentine  of  the  Balm  of  Gilead 
Fii',  {Ahles  hdmmea). 
Storax,  from  the  LiquUlamJmr  orientale. 

OUM-RKSINS. 

Ammoniacum,  an  exudation  of  the  Dorema  ammo- 
niamiin. 

Assafoetida,  a  gum  resin  obtained  1)v  incisioti  from 
the  living  root  of  the  JS\irthe.v  asmfaitida. 

Gamboge,  obtained  from  the  Gavcmia  morella. 

Galbanuin,  from  the  galhanum  officinale. 

My  rrh,an  exudation  of  the  Balmmodendmn  viytrha. 

,  UALSAMS. 

Benzoin,  ol)tained  from  incisions  of  the  bark  of 
Sty  fax  benzoin. 

Balsam  of  Pern,  from  the  Myro^'ylon  Pereirw. 

Balsam  of  Tohi,  obtained  from  incisions  of  the  bark 
ot  Myroxylon  tuluifera. 


Caoutchouc  is  the  hardened  juice  oi  Fictis  elaMica, 
Jatropha  elastica,  Siphonia  cithuohu,  and  other  plants' 

Gutta-perclia  is  the  concrete  juice  of  tlie  perclu, 
(Malay)  tree  the  Isouandra peroha,  a  sapotaceous  plant 


44 


ORGANIC     CIIKMISTUY. 


ALCOHOLS. 

GENERAL  nKKINITION  ANn<"IfAUACTKRISnCS. 

This  name  is  given  to  a  class  of  neutral  bodies  as 
important  as  they  are  numerous.  Their  essential 
characteristic  is  that  ot"  reacting  upon  acids  so  as  to 
form  water  and.  a  class  of  bodies  called  ctha's. 

The  number  of  alcohols  is  very  considerable.  There 
are  several  distinct  varieties  of  alcohol  recognized. 

I.     Those   built  on   the   type  of  one   molecule  of 

water: 

C  II  '  ) 
\\      i  ^'  ^^^^y^  "''  'Jommon  alcohol. 

lolecules  of  water  : 

O.j,  ethylene  alcohol  or  glycol. 


II.  On  two  molecules  of  water 
CJI,"  ) 

Ila       \ 

III.  On  three  molecules  of  water  : 

C  H  ' ' '  i 

"ii*  ^^3'  glvtJerine  and  thus  oil. 

They  may  be  defined  as  bodies  built  on  the  type  of 
one  or  more  molecules  of  water  having  one-half  of  the 
hydi'ogen  replaced  by  a  hydrocarbide  radicle. 

MOXATOSIK.    ALCOHOLS,  . 

or  those  formed  on  the  type  of  one  molecule  of  water. 


i-rMrfiimM<l 


ALCOItOLS. 


45 


rncs. 

1  bodies  as 
ir  essential 
Is  so  as  to 

<  I'S. 

able.  There 
)gnize(l. 
nolecule  of 


ol. 


of  which  ordinary  alcohol  is  the  best  studied,  are 
characterized  by  the  fact  that  they  contain  o'le  atom 
of  oxynjen  only,  and  that  by  reaction  with  the  mono- 
basic acids  thev  Ibrni  onlv  a  sinirlc  ether. 

They  may  be  ohtained  synthetically,  as  well  as  by 
various  indirect  processes. 

Subjoined  is  a  classitied  list  of  tlie  more  important 
monatoniic  alc(»hols: 

FIRST    SrRTKS, 

c„ii,,,o. 

Methyl  alcohol  (woi)d    spirit),  C  TI,  O 
Ktliyl  alcohol,  (spirit  of  ^wine)  V,  U„  O 


iycol. 


Propyl  alcohol 
Butyl  alcohol, 
Amyl  i>,lcohol, 
Setyl  alcohol 
Octyl  alcohol 
Sexdecyl  alcohol 
Ceryl  alcohol 
Myricyl  alcohol 


(',  n«  () 

C^  11,0  o 

c„Tr„o 


SECOND    SKUIKS, 


the  type  of 
!-half  of  the 

ile. 


de  of  water. 


C„II,.(). 


Vinyl  alcohol 
Allvl  alcohol 


TlIIRl)    SERIKS, 


C„II,,._,(). 
ojonieol  alcohol 


G,  H4  O 
CaHeO 


CioILsO 


46 


ORGANIC    CHEMISTRY. 


FoiKTir     SKKIKS, 

Benzyl  alcohol 
Xylyl  alcohol 
Cumol  alcohol 
(^yinol  alcohol 


FIfTII    SKRIEfi, 

C„II,.._sO. 
Cinnyl  alcohol 
Cholesteryl  alcohol 


C:n«o 

Cs  II,oO 

(\  H,oO 
C,oIIuO 


C9  HloO 

c.«ii«o 


MoNATOMic  Alcohols  iiavino  tiik  Gkxeral  Formula, 

METHYL    ALCOHOL,    OR    WOOD-SPIRIT. 

CIIjO^^JJ'lo. 

This  substance  is  found  in  the  liquid  obtained  on 
distilling  wood.  The  distillate  contains  in  addition, 
water,  acetic  acid,  tar,  and  various  oils.  In  order  to 
extract  the  methyl  alcohol,  it  is  again  distilled  and 
that  portion  which  passes  over  at  90°  is  collected ;  this 
is  diluted  with  water,  the  oil  which  precipitates  sepa- 
rated, and  the  liquid  agitated  for  a  considerable  time 
with  olive  oil.  This  oil  is  then  removed,  the  liquid 
redistilled  several  times  and  oidy  that  portion  collected 
which    jjassea    over    above    70°.      On    being   again 


ALCOHOLS. 


47 


o 


w 


uO 


[44O 


Formula, 


<listilled  with  calcium  chloride  it  fiinii>ht's  lutthyl  iil- 
coliol,  nearly  ])urc,  builiiig  at  (](!..'»". 

There  arc  uther  methods  of  rectiiyiii<r  besides  the 
one  here  given. 

This  body  ])ossesses  most  of  the  general  projierties 
of  ordinary  alcdhol.  Under  the  action  of  the  oxides  it 
furnishes  an  aldehyd  and  formic  acid. 

With  the  acids  it  produces  ethers;  viz..  with 

hydrochloric  acid,  methyl  chhn-ide,  CII3CI--    ^,, '  '- ; 
with  acetic  acid, 
methyl  acetic  ether. 


f'"-«'-c,n!o;-0- 


Cnr.oROFoRM,    CirCI;, . 


T. 


obtained  on 
II  addition, 
n  order  to 
stilled  and 
Bcted;  this 
itates  sepa- 
srable  time 
the  liquid 
)n  collected 
)\ug   again 


Methyl  chloride  produces  with  chh)rinc  a  regular 
series  of  ])roducts  of  substitution.  One  (tf  these  terms, 
('IlCl;j,  is  the  very  important  body,  <Moroforiu,  dis- 
covered in  1S31  by  Soubeiran  and  Liebig. 

To  prepare  this  compound,  40  litres  of  water.  A  kilos 
of  recently  slacked  lime,  and  10  kilos  of  cldoride  of 
lime  are  heated  to  40';  l.")00  grams  of  !»0  per  cent, 
alcohol  are  then  added  and  the  retort  luted  with  clay. 

It  is  now  heated  for  a  moment  to  the  boiling  point 
and  the  lire  then  at  once  slackened. 

The  ebullition  having  ceased  there  will  be  found  two 
layers  in  the  receiver.  The  upper  layer  is  formecl  of 
water  and  alcohol,  the  lower  one  is  chloroform  nearly 
l)nre.  The  latter  is  washed  with  water,  agitated  with 
a  dilute  solution  of  jiotassiuni  cju'bonate,  or  with  fused 


48 


OUGANIC     CIIf:MISTUY. 


c-alciuiii  chloridf  tor  tweiity-tour  hours,  iiiid  distilled 
to  loiir-fittlis. 

Cliioroforiii  is  ii  colorless  liquid.  Wiu'ii  tirst  pre- 
pared it  luis  ii  sweetish  penetrating  tuste,  and  nn  tigree- 
able,  ethereal  odor. 

Its  density  is  1.4S;  it  boils  at  GO.o",  is  soluble  in 
alcohol  iind  ether  and  dithcultly  so  in  water. 

It  burns,  thonu'h  not  readily;  its  tlanie  haviu'.;'  a 
jrreen  margin.  It  dissolves  iodine,  sulphur,  plms. 
])liorus.  t'atty  suJ)stanet's  and  resins. 

An  alcoholic  solution  ofpotassa  decomposes  it  into 
chloride  and  foimiate  : 

CliCl,  +  4KIIO       ?,K('l  +  (JIIKO,  +  L>II,(). 

Physiouhucai.  A(TI0X. 

Chlorotbriu  is  at  present  very  generally  used  as  an 
UTiesthetic.  Opinions  as  to  its  manner  of  acting  are 
divided.  Formerly  it  was  thought  that  the  insensi- 
bility produced  was  the  coniniencement  of  asphyxia. 
Since  then  it  has  been  ascertained  that  the  heart,  in 
case  of  poisoning  by  chloroform,  immediately  loses  all 
power  of  contraction,  and  it  is  now  generally  admitted 
that  ]>aralysi9  of  the  muscles  and  nerves  of  the  heart  is 
produ"('d. 

As  the  vapor  of  chloroform  is  very  dense,  care  should 
be  taken  that  in  its  use,  access  of  air  to  the  lungs  be 
not  wholly  ])revented,  or  serious  consequences  m:iy  re- 
sult.    Probably  the  fatal  acciiients  that  have  oos^urred 


ALCOHOLS. 


49 


i«l  tlistilled 

II   lirst  yro- 
d  iiii  iigreu- 

I  soluble  ill 

r. 

I'  liuviu'4'  ji 

iliiir,   plios- 

ost's  it  into 
-  L>II,(). 


TTiav,  in  some  instances  at  least,  bo  attributed  to  lack 
of  care  in  this  rei^^ard. 

It  is  of  great  iii)])()rtance  that  the  chloroform  used 
should  be  quite  i>iire.  In  some  cases  it  has  been  found 
to  have  undergone  spontaneous  decompositioii  after 
exposure  to  a  strong  light.  It  ought  to  communicate 
no  color  to  oil  of  vitriol  when  agitated  with  it.  The 
lifjuid  itself  should  be  free  from  color  or  any  chlorous 
odor.  "When  a  few  drops  are  allowed  to  evaporate  on 
the  hand  no  unpleasant  odor  should  i-emain. 

Shuttleworth  (^100,  4,  339)  states  that  partially  de- 
composed  chloroform  can  be  rectified  by  agitating  it 
with  a  solution  of  sodium  hypo-sulphite. 


used  as  an 
acting  are 
le  insensi- 
'  asphyxia. 
e  heart,  in 
ly  loses  all 
y  admitted 
;he  heart  is 

2are  should 
e  lungs  be 
es  m:iy  re- 
e  oot-'urred 


ORDIXAIIY  ALCOHOL. 
Ethvlic,  oij  Vixie  Alcohol. 


Formula:  C<UJ). 
Density  of  vapor  2:!. 
Density  .81. 
Boils  at  78.4°. 
Cannot  be  solidified. 


It  is  prepared  by  the  fermentation  of  saccharine 
liquids  at  a  temperature  of  25"  to  80",  in  the  presence 
of  a  small  quantity  of  a  ferment.  Cane  sugar  does 
not  directhj  become  alcohol  under  the  influence  of  a 
ferment.     It  is  firs.*^^  transformed  into  two  other  sugars. 

lit.  &  ' 


glucose  and  levulos  \ 


50  ORGANIC     CHEMISTRY. 

c,,u,>,On+  ii,c)=c,,ir,,(\=cjT,,()«. 

Glucose.  Levuloae. 

Ill  its  final  fermentation  nearly  all  the  siimir  is 
clianged  into  alcohol  and  carbon  dioxide, 

C«II,i)«=2C,II,,()+liC0,. 

This  equation  accounts  for  the  transformation  of  O-t 

^    to  90  per  cent,  of  the  sugar  employed,  hut  besides 

alcohol   and   carbon  dioxide,  succinic  acid   is   always 

formed  as  well  as  <flyoerine,  and  in  most  cases  ''  fusel 

oil,"  consisting  chiefly  of  aniyl  alcohol. 

Fermentation  is  a  phenomenon  correlative  with  the 
development  and  growth  of  cells  of  the  fungus  Myco- 
derma  (Torula)  cerevisim  which  constitutes  yeast. 
Suinetimes  the  sugar  is  furnished  as  a  natural  product 
by  fruits;  often  glucose  is  produced  from  the  starch 
of  cereals,  potatoes,  etc.,  and  then  changed  into  alcohol 
afterwards.  Corn  is  the  leading  original  source  in 
this  country. 

Alcohol  obtained  by  fermentation  is  concentrated 
by  distillation.  This  o])eration  is  performed  in  retorts, 
the  constmction  of  which  is  based  u])(m  a  principle 
developed  by  A.  de  JVIoiitpellier,  and  improved  by 
Derosne,  Dubrunfaut  and  others.  The  object  is  to 
prevent  the  distilling  over  of  the  water  with  tlie  alco- 
hol, and  is  quite  well  accomplished  by  the  improved 
methods  now  employed.  The  details  are  not  suited 
to  the  scope  of  this  work. 

The  application  of  this  rational  method  of  distilling 


ALCOHOLS. 


51 


Ob. 

ose. 


he  sugar  is 


nation  of  94 

l)iit  besides 

d   is   always 

cases  ''  fusel 

tive  with  the 
iiigus  Mijco- 
itutes  yeast, 
ural  product 
1  the  starch 
into  alcohol 
a,l  source   in 

concentrated 
ed  in  retorts, 
a  principle 
inproved  by 
object  is  to 
ith  the  alco- 
lie  improved 
■0  not  suited 

[of  distilling 


admits  of  obtaining  liquids  containing  up  to  90  ])or 
cent,  of  alcohol,  but  it  is  difficult  to  go  beyond  that 
point  of  concentration. 

In  order  to  prepare  alcohol  more  concentrated,  sub- 
stances having  a  great  avidity  tor  water  must  be  used. 
Calcium  chloride  is  not  suitable,  as  it  unites  with, 
the  alcohol.  Anhydrous  sulphate  of  copper,  carbon- 
ate of  potassium  or  quicklime  do  not  produce  absolute 
alcohol.  But  it  is  very  rai-e  that  perfectly  anhydrous 
alcohol  is  required.  Alcohol  of  97  per  cent,  is  obtained 
in  treating  alcohol  of  85  per  cent,  duringtwodays  with 
lime,  (jr  butter,  with  a  sixth  or  seventh  pail  of  its  weight 
of  dry  potassium  carbonate,  and  then  distilHug.  If  it 
is  desired  to  procure  absolute  akiohol,  wvy  conci-n- 
trated  alcohol,  is  treated  with  caustic  baryta  until  the 
liquid  is  colored  yellow  and  then  distilled. 

Alcohol  in  fresh  bread  made  with  yeast  has  been 
found  by  Bolas  (8-27-271)  to  the  amount  of  .314  per 
cent.  Slices  of  bread  a  week  old  contained  .12  to  .13 
per  cent. 

Absolute  alcohol  is  a  colorless  liquid,  more  limjjid 
than  water,  of  an  agreeable  odor  and  a  burning  taste. 
It^  boils  at  78.4",  is  neutral,  combustible  and  burns 
with  a  flame  but  little  luminous.  It  heats  m\  coming 
in  contai't  with  water,  and  attracts  the  moisture  of  the 
air  very  rapidly. 

It  contracts  upon  mixing  with  water;  the  i;i!ix- 
imum  of  sontraction  takes  place  at  a  temperatuiv  of 
lo°wheu  52.3  vol.  of  absolute  alcohol  are  mixed 
with  4T.7  vol.  of  water;  instead  100  vol.  one  obtains 


S2 


ORGANIC     ClIKMISTUY 


06.3   vol.     At  the  moment  of  admixture  munerous 
iiir  bubbles  escape  and  the  nuxture  becomes  heated. 

The  ak-oliolic  streniith  of  the  liquids  consumed  as 
beverunes  varies  considerablv. 

Madeira  wines,  about  20  per  eent. 

:M"ala«;.".         "        "      14  to  16        '• 


Bordeaux 

u 

5  to  12 

(( 

Elune 

a 

10  to  12 

(( 

California 

li 

7 

t( 

Cider 

2  to    7 

if 

Beer 

Ito    8 

- 

Spirits  lire  distilled  from  fermented  liquids;  hmnthj 
fi'om  wine;  trhlsk'tj  from  a  masli  of  corn  or  rve  ;  rinn 
from  molasses,  etc.  They  contain  abo\'t  50  per  cent, 
of  alcohol. 

The  term  proof  spirits  was  originally  given  to  al- 
cohol sutHeiently  strong  to  tire  guupowdi'r  when 
liglited.  The  strength  of  proof  spirits  now  varies  in 
diftereiit  localities,  and  it  wouhl  bo  well  were  this 
and)iguous  designation  no  longer  eiiiploved. 

Alcohol  dissolves  the  caustic  alkalies,  certain  ni- 
trates, chlorides  and  other  salts,  also  various  gases. 
With  some  of  these,  genuine  chemical  combinations 
are  ])rodnced,  and  not  mere  solutions;  this  is  the  case 
with  calcium  chloride  and  magnesium  nitrate. 
Alcohol  can  be  mixed  with  ether  in  all  proportions; 
it  dissolves  the  resins,  essential  oils,  and  a  great  num- 
ber of  oilier  organic  bodies. 

The  chemical   ))roperties  of  alcohol  are  very  inter- 


ALCOHOLS. 


6& 


mimermis 

s  hoatt'd. 
iiiMuiiu'cl  us 


("lit. 


ds;  hmnihj 
■  ryv  ;  7'uiit 

0  per  coiit. 

riven  to  al- 
idi'i"  when 
v  varies  in 

1  woro  this 
.1. 

certain  ni- 
ious  ^ases. 
nibinatioiis 
is  tlio  case 
a  nitrate, 
roportions; 
yreat  uuiu- 

verv  inter- 


estinjr.  Vapor  of  alcoliol  is  decomjiosed  on  passinj? 
tliroui^li  a  tube  lieated  to  redness;  hydrogen,  niarsii- 
.ijas,  oxide  of  carbon,  small  quantities  of  naplitluiliii, 
bi'iizol,  and  phenol  are  formed.  In  presence  of  air 
and  Avater  it  slowly  oxidizes  and  yields  acid  com- 
pounds. This  action  is  rapid,  if  a  hot  spiral  of  ])lati- 
mnn  is  phiced  in  the  alcoholic  vapor. 

Experiment. — Place  a  small  platinum  spiral  in  the 
wick  of  an  alcohol  lamp,  light  and  then  blow  out  the 
flame.  It  will  be  seen  that  the  spiral  remains  incan- 
descent. Spongy  platinum  acts  still  more  energetically; 
if  very  concentrated  alcohol  is  poured  drop  by  drop  into 
a  capsule  containing  spongy  platinum,  or  platinum 
black,  it  will  be  seen  to  redden,  fumes  are  produced  and 
un  ,'''id  liquid  is  formed  containing  chiefly  aldehyd 
tt>  -icacid.     The  same  oxidation  occurs  if  diluted 

fi  M'.  ;  iS  exposed  to  the  air  in  the  presence  of  mother  of 
vinegar,  a  cryptogamic  plant,  (Mycodrrma  accti).  In 
fact,  this  is  the  basis  of  the  manufacture  of  wine-vin- 
egar and  alcohol. 

Fuming  nitric  acid  reacts  upon  alcohol  with  ex- 
plosive energy.  Aldehyd  is  formed,  also  acetic  ether, 
nitrous  ether  and  acetic,  formic,  glycollic,  oxalic  and 
carbonic  acids.  Alkaline  hydrates  attack  alcohol  even 
in  the  cold  potassium  acetate  being  the  chief  product 
formed.  If  alcoholic  vapor  is  made  to  pass  over  lime 
heated  to  250°,  hydrogen  gas  and  calcium  acetate 
are  produced;  the  latter  is  decomposed  at  a  more 
elevated  temperature  into  marsh  gas  and  water.  If 
silver  or  mercury  is  dissolved  in  nitric  acid,  and 
90  per  cent,  alcohol  added  to  the  cooled  solutions,  a 


--i-rr'  I  -uriiiiai^-itifcua-iji 


u 


ORGANIC    CHEMISTRY. 


11! 


lively  ebullition  results,  and  a  crystalline  precipitate  is 
deposited  which  explodes  at  185°,  or  by  percussion. 
This  body  is  the  fulminnte  of  silver  or  mercury,  re- 
spectively, which  is  considered  as  derived  from  methyl 
cyanide,  CHjCy,  by  the  substitution  of  1  molecule  of 
nitryl,  and  of  1  atom  of  mercury,  or  2  of  silver  for  3 
atoms  of  hydrogen.  The  formulae  are  C(NO,)HffCy; 
C(N02)Ag,Cy. 

Potassium  attacks  absolute  alcohol,  and  is  dissolved 
liberating  hydrogen;  on  cooling,  potassium  ethylate  is 
deposited.  Sodium  acts  in  the  same  manner.  These 
compounds,  if  brought  in  contact  with  water,  regenerate 
alcohol  and  the  respective  alkaline  hydrates. 

Acids  attack  alcohol  and  furnish  compound  ethers, 
which  we  will  study  later.  0/one,  according  to  A.  W. 
Wright,  (80— [3]7— 184)  oxydizes  alcohol  to  acetic  acid. 

Physiological  Action  of  Alcohol.  Uses  of  Al- 
cohol.—Alcohol  coagulates  the  blood;  injected  into  the 
veins  it  produces  instantaneous  death.  It  is  a  very 
powerful  poison,  as  are  all  alcohols  of  the  series 
CnH2„+>0.  Rabuteau  (9—81—631)  has  shown  that 
they  are  more  poisonous  in  proportion  as  their  mole- 
cules are  complex.  Cases  hiive  been  observed  where  a 
large  dose  of  alcohol  has  caused  death  in  half  an  hour. 

The  worse  than  worthless  character  of  distilled 
liciuors  as  beverages  is  no  longer  an  open  question. 
With  regard  to  their  value  as  food  or  medicine,  a  more 
authoritative  or  com])eteut  expression  of  opinion  can- 
nut  1)0  desired  than  that  of  the  iTiternational  Medical 
Congress,  which  at  its  session  in  Philadelphia  in  1876, 
said : 


ALCOHOLS. 


65 


recipitate  is 
percussion. 
mrcury,  re- 
om  methyl 
nolecule  of 
silver  for  3 
^08)HgCy; 

is  dissolved 

ethylate  is 

ler.     These 

,  regenerate 

und  ethers, 
y  to  A.  W. 
acetic  acid. 

5E8   OF  Al- 

;ed  into  the 
is  a  very 
the  series 
hown  that 
heir  mole- 
ed  where  a 
fan  hour. 

f  distilled 
1  question, 
ne,  a  more 
)inion  can- 
al Medical 
ia  in  1S76, 


"1.  Alcohol  is  not  shown  to  have  a  definite  food 
value  by  any  of  the  usual  methods  of  chemical  analy- 
sis or  physiological  investigation. 

"  2.  Its  use  as  a  medicine  is  chiefly  that  of  a  cardiac 
stimuhmt,  and  often  admits  of  sul).stitution. 

"  3.  As  a  medicine,  it  is  not  well  fitted  for  self-pre- 
pcription  by  the  laity,  and  the  medical  profession  is 
not  accountable  for  such  administration,  or  for  the 
enormous  evils  arisinji;  therefrom. 

'••i.  Tiie  purity  of  alcoholic  licpiors  is,  in  general, 
not  fis  well  assured  as  that  of  articles  usedf  )r  medicine 
should  be.  The  vari(nis  mixtures  when  used  as  medi- 
cine, should  have  delhiite  and  known  composition,  and 
should  not  be  interchanged  promiscuously." 

The  dissolving  power  of  alcohol  renders  it  very  ser- 
viceable in  the  arts.  Solutions  in  this  menstruum  are 
called  alcohuliG  tinctures.  Only  the  purest  alcohol 
ought  to  be  used  in  pharmacy,  though  of  course,  various 
strengths  are  requisite,  as  it  should  be  of  a  degree  to 
suit  the  nature  of  the  matter  to  be  dissolved.  If  the 
su1)stance  to  be  treated  is  a  re?in,  or  some  substance 
absolutely  insoluble  in  water,  a  very  concoutrated  alco- 
hol is  preferable.  A  weaker  alcohol  is  made  use  of,  if 
the  nuitter  is  one  that  is  soluble,  both  in  alcohol  and 
water. 

Alcohol  acts  notoidy  as  a  solvent,  but  also  as  a  2)re- 
ventative  of  decay.  This  is  a  ])roperty  which  renders 
it  especially  valuable  in  the  preparation  of  remedies. 


»pi«" 


Iliyl-limn 


-^r-n 


~^ift3^rl'fi^\^ 


56 


ou(;anic  chkmistuy 
AMYL  ALCOHOL. 


(\M,o 


11 


O. 


fli/nonymn:     Fouskl  (ou  Fusei.)  Oil,  P(rrATo  Si'ikit. 

Tho  amylie  cuinixMiiuls  derive  their  luune  from 
Ami/lum,  starch,  the  chief  constituent  of  tlie  potato. 
Theyare  formeil  in  sotne  proportion  in  ahnost  every  in- 
stance of  alcoholic  fermentation  of  6ui>;ar.  Aniylic 
alcohol  is  usually  prepared  on  fractionally  redistilling 
the  oil  which  remains  when  the  alcohol,  prepared 
from  potatoes,  barley,  corn,  etc.,  is  distilled.  The  ])ro- 
duct  which  comes  over  at  i;J2",  is  that  collected. 
Cahoiirs  and  JJ;ilard  first  established  the  analoirv,  in 
constitution  and  i»roperties,  of  this  compound  with 
ordinary  alcohol.     It   is  a  monatomic  alcoh(»l,  ffivin"- 

•    1  •  1  •     •  '  £3  » 

With  oxKlizing  re-agents,  valeric  acid. 

C3I  [,,(^+0,  :^  C,,I1„,0,+ 11,0, 

Amylic  alcohol.  Valeric  acid. 

and  with  acids,  coin])ound  ethers,  as 

Chloride  of  amyl,  CsIInCl. 

Acetate  of  amyl  or  amyl-acetic  ether,        ,,  .f'k  ^  O. 

CallgO   \ 


'nffATO  SriKIT. 

r  luiine  from 
of  tlie  ])Otatu. 
most  every  in- 
gav.  Amjlic 
lly  redistillincr 
hoi,  prepared 
ed.  Tlie  ])ro- 
luit  collected, 
lie  analogy,  in 
inpomid  with 
Icohol,  giviiig 


■O, 


cjr„ci. 


o. 


ALCOHOLS. 

M(  )XATOMIC  ALCOHOLS. 

Having  the  general  Formula  (\,H,,„(). 

Allymc  .a  i.coiio.     CaHjO  =  L\1L,  ,  ^^ 


57 


"{i1 


This  is  a  body  giving  the  same  reactions  as  ordinary 
alcohol.  The  radicle  it  contains  is  the  same  as  tlmt 
in  the  triatomic  alcohol,  glycerine.  Among  its  deriva- 
tives there  are  two  which  are  of  considerable  impor- 
tance: 


Allyl  sulphide,  p'"--  I  s 


f 

Sulpho-cyanide,  ^sljs )  g_ 

The  former  is  oil  of  garlic;  the  latter  oil  of  mustard. 
(^IL  OF  (iAKLii;  is  pi-epared  by  the  following  method: 
allylic  alcohol  is  treated  with  phosphorus  iodide  which 
furnislies  allyl  iodide  C3H5L  This  iodide  is  afterwards 
mixed  with  an  alcoholic  solntion  of  potassium  sulphide 
and  the  whole  is  distilled;  the  product  which  passes 
over  is  identical  with  the  essential  oil  ol)tained  in  dis- 
tilling garlic,onions,  assafojtida,  etc.,  with  water. 

OIL   OK   IICSTAKD.   OK   SULPHO-CYAMUK    OF    ALI.YL. 

This  body  is  ])repared  by  causing  iodide  of  allyl  to 
react  upon  ix.tassium  sulpho-cyanide, ^'jj  U,  and  may 
be  regarded  as  sulpho-c-yauic  ucid,^JJ  }■  S,  luiving  the 


*^ 


m 


OltGANIC     OIIKMISTItY, 


livdrogoii  replaced  by  tlie  radicle  <jf  allyl  alcohol,  CslL,. 
Tliu  product  which  distills  over  is  an  irritating  liquid 
which  boils  at  145",  like  the  oil  prepared  froiri  iiiiis- 
tard  directly.  This  substance  may  also  be  obtained 
by  the  action  of  allylic  alcohol  upon  ])(>tassiuni  sul- 
pho-cya-.iide.  It  is  likewise  obtained  by  the  fernienta- 
tion  of  mustard  seeds. 

Sul])ho-cyanideof  allyl  does  not  exist  already  formed 
in  black  mustard  (Shiajns  luyro),  but  according  to 
Bussy,  its  fornuition  is  due  to  a  particular  ferment. 

Oil  of  mustard  combines  directly  with  ammonia, 
forming  a  crystalline  substance  called  thioshiiuihilnc, 
CiH^XoS,  which,  in  contact  with  mercuric  oxide, 
changes  into  an  alkaloid  called  sinnaniine,  of  which 
the  composition  is  C4H0N...  It  reacts  upon  lead  oxide 
producing  a  substance  called  s'mapoUne  whose  formula 
is  C;K,,N,(). 


B( 


)RNKO    CAMl'UOR,    OR    BOilXEOL    C,oHis<^- 


This  body  exudes  from  the  dryohalcmoj)>i  cmnphora 
(Borneo).  It  is  crystalline  and  has  an  odor  between 
that  of  camphor  and  pepper.  It  fuses  at  105°,  and 
boils  at  about  220".  It  is  dextrogyrate.  Heated  with 
nitric  acid  it  furnishes  common  campln)r  CioHsO. 


DIATOMIC    ALCOHOLS  OK  GLYCOLS, 

Ordinary  Glycol,  (CjH^)  — 0.— H2=CJIe  0. 
Propyl  "      (C,H,,)  -O.-IL^C^H^  0, 


I  alcohol,  CslTs. 
•ritating  liiiuid 
red  from  iiiiis- 
50  be  obtaiiu'd 
])ntassiuiii  siil- 
y  the  tenuenta- 

ah'oady  formed 
it  according  to 
dar  ferment, 
kvith  ammonia, 
7(  loshinam  In  c, 
lerciiric  oxide, 
nine,  of  which 
i])on  lead  oxide 
?  whose  formula 


yiops  C'iiHj)hora 
I  odor  between 
3S  at  195°,  and 
!.  Heated  with 
or  CoHeO. 

!OL8. 


,=CAi,  0, 
o— C,Hs  0., 


ALCOHOLS.  69 

Butyl  Glycol,  (C,H,)  _0,-H„=C,H,„0., 

Amyl        "  (C,H,„)-0,-H,-C,H,„0: 

Hexyl       '•  (C„H, ,)-()„ -H,=("„H,;o.; 

Oetyl        "  (C.H.«)-03-H,=C«H,«o:. 

TRIA'nmUJ    ALCOHOLS. 

Glycerine,  (C3H.)-0;,-H3=C,H,03. 

TKTRATOMKJ    ALCOU0L>i. 

Erythrite.  ((:;,H„)-0,-H,=C,H,„0,. 

OTUKK   COMIM.KX    Af.COHOI^. 

Glucose  and  its  isomeri.les,  (C„H,)-0„-H„  =C„H,  „0o 
Manuite,  -        -      (C„H,)-0«-H„=(',H,;o«. 

Dulcite,         -        -       -    (C.H«)-0«-H«-C«H,,Oe. 
(juercite,  )  r,  tt  /^       ^CH  ^    i  ^ 

ORDINARY    GLYCOL. 

Clio  =^^^^i)j  '  n 

The    discovery  of    the  glycols  was   an  event  of 
great  imi)ort.ince.     It  was  aclueved  hy  Wurtz  in  185(5, 
and  the  glycol  of  v/hich  we  are  treating  was  the  lirst 
discovered. 

In  a  flask  surmounted  by  a  condenser,  two  parts  of 
])otassimn  or  sodium  acetate,  are  dissolved  in  weak- 
alcohol  and  one  ])art  of  ethylene  bromide  added.     This 


'  i 


60 


OROAXIC    CIIEMISTBY. 


mixture  islieatofl  in  a  water  bath  as  long  as  the  pre- 
cipitate of  alkaline  bromide  continues  to  form,  care 
beina:  tai<eii  at  the  same  time  to  keep  the  worm  well 
C(Miletl,  in  order  that  the  vapors  of  alcohol  may  contin- 
ually How  back  into  the  fla>k.  The  alcohol  is  distilled 
oft'  in  a  water  bath,  and  the  residue  afterwards  also 
distilled  at  a  higlier  temperature,  and  that  part  col- 
lected which  passes  over  between  140"'  and  200° .  This 
portion  which  contains  nionacetic  glycol,  is  heated 
with  a  saturated  solution  of  l)aryta  until  the  lic^uid 
acquires  a  strong  alkaline  reaction.  The  excess  of 
bar^'ta  is  removed  by  passing  carbon  dioxide  through 
the  solution  which  is  then  filtered  and  evaporated. 
The  barium  acetate  is  ])recipitated  coini)letely  by  strong 
alcohol,  and  the  alcohol  subseqnentlv  removed  by  dis- 
tillation. Tlie  retort  is  now  heated  in  an  oil  bath,  and 
that  portion  set  aside  which  boils  above  150°.  This  is 
redistilled  and  the  distillate  between  190°  and  108° 
is  the  product  sought.  Zeller  and  Iluefner  have  lately 
(18,  10,270)  obtained  the  ]>urest  glycol  by  simply  heat- 
ing a  solution  of  potassium  carbonate  with  ethylene 
bromide. 

Glycol  is  a  colorless,  odorless  liquid,  somewhat 
viscid  and  having  a  sweetish  tas*?.  Its  density  is 
1.12;  water  and  alcohol  dissolve  it  in  all  proportions. 
Ether  dissolves  it  with  difficulty. 

It  is  not  oxydized  in  the  air  under  ordinary  con- 
ditions, but  if  dilute  glycol  be  made  to  fall  on  plati- 
num black,  it  becomes  heated  and  is  transformed  into 
glycoliG  acid.     Its  equivlence  is  shown  by  the  follow- 


ALCOHOLS. 


(51 


as  the  pro- 
t(»  form,  cure 
le  worm  well 
1  may  coiitin- 
rol  is  distilled 
terwanis  also 
that  part  Ci>l- 
1  aoO" .  This 
ol,  is  lieated 
til  the  licjiiid 
lie  excess  of 
xxide  through 
I  evaporated, 
[■el y  by  stroiijr 
iioved  by  dis- 
oil  bath,  and 
150°.  This  is 
30"  and  108° 
er  have  lately 
'  simply  heat- 
kvith  ethylene 

id,  somewhat 
[ts  density  is 
I  proportions. 

ordinary  con- 
fall  on  plati- 
iisformed  into 
by  the  follow- 


ing:    glycol    attacks    siKlium    forming   two    sodiujii 
glycols; 


Kali    ***^'  .NaM^'^- 


These  glycols  furnish  two  ethyl  glycols  on  being 
heated  with  ethyl  iodide. 


c^,ii.,r^-* 

Etliyl-alycol. 


Dlelhyl.glycol. 


AVith  hydrogen  bromide  it  furnishes  two  different 
products  according  to  the  number  ot  molecules  of  UBr 
taken. 

C,lUO^+  HBr  -  C,UJivO  +  II,(). 


Monobromhydric 

uther. 


CJI,0,  +  2irBr=C.JI,Br+  2II,0. 


Kthvluiifc 
bromide. 


It  is  evident  tliat  mixed  ethers  may  be  obtained  by 
treating  glycol  not  with  two  molecules  of  the  same 
acid,  but  with  two  molecules  of  ditierent  acids.     Thus 

aceto-chlorhydric glycol  is  formed, .,  tt  J.-J!'  J-  O. 


rr 


02 


ORGANIC    CHEMISTRY 


These  ethers,  in  the  presence  of  alkalies,  are  re- 
formed into  their  respective  acids  and  glycol,  in  the 
.same  manner  in  which  ethers  of  ordinary  alcohol 
regenerate  alcohol. 

Monochlorhydric  and  aceto-chlorhydric  glycol  form 
an  exception  to  this  rule;  they  form  oxide  of  ethylene 
in  presence  of  alkalies. 

OXIUK  OF  KTIIYLKNE,   0,11,0, 

a  polymer  of  (('.,II,)2(%,  is  related  to  glycol  as  ordinary 
ether  to  alcohol.  It  is  not  obtained  like  the  latter  by  the 
action  of  hydrogen  sulphate  on  the  alcctholic  coiiipdund, 
but  is  produced  by  the  action  of  potassa  on  mono 
chlorhydric  glycol.  A  solution  of  potassa  is  gradually 
poured  iuto  chlorhydric  glycol  i)laced  in  a  glass,  or  a 
tubulated  retort. 


KHO  +  CgHgClO  =  KCl  +  H2O  +  C2H4O. 

The  oxide  of  ethylene  distills  over  with  the  water; 
the  latter  is  absorbed  by  causing  the  vapors  to  pass 
through  a  flask  containing  anhydrous  calcium  chloride, 
and  the  oxide  is  condensed  in  a  receptacle  placed  in  a 
refrigerating  mixture. 

It  is  a  colorless,  ethereal,  fragrant  liquid;  boiling  at 
13°.  Its  density  is  0.89.  Ethylene  oxide  is  very  solu- 
ble in  water,  alcohol  and  ether.  It  burns  with  a  lumin- 
ous flame  and  reduces  silver  salts.  It  has  the  compo- 
sition biit  not  the  properties  of  aldehyd,  of  which  it  is 
an  isomeride. 


Ill 


ALCOHOLS. 


<)3 


lies,  iire  re- 
vool,  in  the 
mrv  alcohol 


glycol  form 
)  of  ethylene 


Oxide  of  ethylene  is  a  very  remarkable  body.  It 
combines  directly  M-ith  oxygen,  liydroi;eu,  chlorine  and 
bromine,  also  combineii  directly  with  acids,  ofcen  even 
with  the  disengagement  of  heat,  forming  the  ethers  of 
glycol  and  polyethylenic  alcohols.  This  body  is  there- 
fore a  true  non-nitro^euous  basic  oxide. 


1  as  ordinary 

latter  by  the 

c  compound. 

Hi  on  mono- 

is  gradually 

a  glass,  or  a 


Ii  the  water; 
poi's  to  pass 
um  chloride, 
i  placed  in  a 


1;  boiling  at 
is  very  solu- 
rithalumin- 
1  the  compo- 
f  whicii  it  is 


()4 


oh(;a.\ic  cjikmistry. 


TPJ ATOMIC  ALCOHOLS  OR  GLYCERINES. 


,"  i 


Oruinaky  Gi,y(  krixe,  CaHgO;,  =^'{['  |  <>  • 

This  body,  discovered  by  Scheele,  in  1770,  and 
called  by  him,  on  aceoiiiit  of  its  sweet  taste,  the  sweet 
principle  of  oils,  has  been  specially  studietl  by  Chevreul 
and  by  Pelonze.  Bei-thelot  discovered  its  real  nature 
and  proved  it  to  be  a  triatoniic  alcohol. 

Glycerine  is  prepared  by  decomposing  neutral 
fatty  bodies,  in  the  soap  and  candle  industry  by  alka- 
lies, or  better  still  by  superheated  steam.  {Tihjhinans 
'process.)  It  is  obtained  in  pharmacy,  whenever  lead 
I>laster  is  prepared  and  remains  in  the  water  with 
which  the  latter  is  washed. 

It  is  nmch  emi)loyed  in  pharmacy  and  perfumery 
and  as  a  solvent  for  many  substances,  ("rude  glycer 
ine  may  be  purified  by  boiling  with  ain'nial  charcoal 
and  filtering  before  being  evaporated  to  the  rccpiired 
consistency.  The  best  ])roces8  consists  in  distilling  the 
crude  condensed  glycerine  in  a  current  of  steam.  Pas- 
teur has  shown  tlnit  glycerine  is  ]>roduced  in  a  very 
small  (pnintity  in  alcoholic  fermentation.  AVe  owe  to 
Wurtz,  a  remarlciible  synthetical  reproduction  ofglyccr 
iiie.  Pi(»pyl«.'ue  (';,1I,.,  furriishes an  iodide ( ';,II;,I,  called 
iodide  of  idly].     This  bixly  produces  with  bromine  the 


ALCOHOLS. 


65 


rCEPJXES. 


I,  ■( 

1:,    » 


0 


in  1770,  and 
xste,  the  sweet 
tnl  by  Chevreul 

its  real  nature 

josing  neutral 
lustry  by  alka- 
.  {Tlhjhinaii's 
tvhenever  lead 
le    water   with 

ind  pert'uinery 
("rude  glycer 
liuial  charcoal 
u  tlie  rccjnired 
n  distilling  the 
t"  steam.  Pas- 
iced  in  a  very 
1.  AVe  owe  to 
ctiou  (if  gl veer 
^  (';,!  I ;,!,' called" 
h  bruiiiiue  the 


coinpomid    CJI-.nr,,   wliich,    treated    with  potassa,   or 
oxide  of  silver,  yields  glycerine. 

CJi^Bra+SKlIO  -=  3  KBr.+(l,IIA 

(jlycerine. 

Glycerine  is  a  syrupy  liquid,  colorless,  of  a  sweetish 
taste  and  destitute  of  odor;  its  density  is  1.28  at  15". 
Sarg  has  obtained  crystals  of  glycei-ine,  whose  angles 
have  been  measured  by  Victor  Lang  (2  l.>2-037). 
They  are  rhombic  in  form  and  very  deli(piesoent.  Glyc- 
ei-ine  is  soluble  in  alcohol  and  water  in  all  pi-opoi-- 
tions;  it  is  not  dissolved  by  ether.  It  dissolves  alka- 
lies, alkaline  sulphates,  chlorides  and  nitrates,  copper 
sulphate,  silver  nitrate  and  many  other  salts. 

Glycerine  distills  at  280°,  but  is  thereby  partially 
decomposed.  It  may,  however,  be  distilled  in  a 
vacuum  without  cliiinge.  It  is  decomposed  nt  a  tem- 
perature above  300",  and  oils,  iiiHammable  gases, 
carbon  dioxide,  and  a  ])rotiuct  Vc-ry  iri-itatiiig  to  the 
eyes,  called  acrolein,  acrylic  aldehyd,  are  formed; 
this  last  substance  may  be  obtained  pure  by  distilling 
glycerine  with  sulphuric,  or  phosjihoric  acid.  The 
formula  of  acrolein  is  C,l  1,0.,;  it  is  jdso  produced  in 
the  dry  distillation  of  all  fatty  bodies  wiiich  contain 
glycerine.  If  glycerine  be  made  to  fall  drop  by  drop 
upon  platinum  black,  it  unites,  like  alcohol  and 
glycol,  with  ().,  and  (jlijcer'ic  aot'd  is  formed. 

C,,Il8(),  +  O,-{',lI,,0, -1-11,0. 

The  oxidation  of  the  glycerine  does  not  stop  here; 


I  ■ 


i 

:  i  : 


1 


f    ,i 


6d 


ORGANIC     CIIKMISTUY. 


there  is  siibse(iiieiitly  formed,  acotie,  formic,  and  car- 
bonic, but  cliietiy  oxal'c  acid.  The  action  of  acids  on 
glycerine  demonstrates  two  facts;  first,  that  glycerine 
is  an  alcohol;  second,  that  it  is  a  triatomic  alcohol. 
On  treating  glycerine  with  hydrochloric  acid  the  first 
reaction  is  similar  to  that  between  uleohol  and  this 
acid, 

iici+cyiA-t^jr^cio.+ii.o. 

Monocblo  bydric  etiier, 
or 
Monoclilorliydriii. 

The  continned  action  of  ]))iosphoions  perchloride 
upon  glycerine,  ov  the  dichlorliydrate  of  glycerine, 
effects  the  elimination  of  additional  molecules  of  water 
and  the  formation  of  trichlorhydrin. 

3lICl+C:,IIs():,=:C3lI,,Cl ,  +  8(  11,0) 

Triciilorhydriu. 

Bertheltit  has  studied  the  acetines,  butyrines  (tri- 
butyrine  exists  in  butter),  vaierines,  a;i(l  many  other 
ethers  of  glycerine.  If  glycerine  is  mixed  with  cohl 
nitric  acid,  and  sulphuric  acid  aildcd  drop  by  drop,  an 
oily  sul)s,an;e separates  out  which  is  ti  iiilfroffliicei'inn 
C;JI.,iNO.V,0:i.  This  body  detonates  with  great  vio- 
lence. It  acts  very  energetically  on  the  system.  A 
few  drops  placed  on  the  tongue  ]>r.>(luco  violent  me- 
grim. Glycerine  forms  compounds  with  lime  anal- 
oirctus  to  those  formed  by  sugar,  according  to  P.  Car- 
les,   1-  174  87). 


ALCOHOLS. 


07 


ic,  and  cur- 
of  acids  on 
t  glycerine 
lie  alcohol, 
cid  the  first 
)1  and  this 


pei'chloridc 

glycerine, 

[es  of  water 


I  vi'ines  (tri- 
naiiy  otlicr 
I  witli  cold 
by  drop,  an 
ivf/Ii/ceri/ie 
great  vio- 
•ysteni.  A 
violent  ine- 
linio  anal- 
X  to  P.  Car- 


TsKs. — The  uses  id'  glycerine  in  the  arts,  and 
especially  in  i)hannacy,  are  numerous  and  important, 
many  of  which  are  ba:<ed  upon  the  solvent  power  of 
this  coiupouiid.  Henry  Wurtz  (31-105-5^)  has  made 
valuable  suggestions  as  to  its  economical  applications. 

TAKI.K   SlIOWINO  TUB   M()[.UI1II.1TY  OP    SOME    CIIKMICAI.S    IN  OLI  CKllINK,   (PROM 

KLEVEK.)  ONK   IIINIIIIKI)   I'ARTa  OP  lil.YCEIllNB   DISSOLVE  TUE  ANNEXED 

VUANTrriES  OF   THE  t'OIXUWINd  CUBMIOALS: 


Arsenou'^  oxide, 
Arsenic  oxiile, 
Acid,  IxMi/.oic, 

■'      oxalic, 

"       tAUU!c, 

Aliini, 

Ammouinm  cirbonate, 

cliloride. 
Antimony  nud  potaeeium  tartrate, 
Atropin, 

Airiipiii  Hulpliate, 
Itarliim  cbluride, 
Uniria, 
Cinchonia, 

"  eulplifttc, 

Copper  nceliite, 

"     sulplmte, 
Iron  and  potassium  tartrate. 
"    lactate, 
"    siilptiate, 
Sreri'.uiic  chloride, 
Meicui'ous  chloride, 
Iodine, 
Morphia, 
Morphia  aceliile, 

"        clilorhydrito, 
I'liosphoius, 
I'liinihic  acetate, 
Potassium  arHunnto, 

"  chlorate, 

"  bromide, 

"  cyanide, 

"  iodide. 


Quiiiia, 


tauuato. 


30.00 

ao.oo 

lO.OC 
15.00 
60.00 
•lO.OO 
20.00 
20.00 
5.50 
8.00 

a3.oo 

10.00 

2.w'5 

O-.'JO 

6.70 

10.00 

30.00 

8.00 

16.00 

25.00 

T.50 

2T.00 

1.90 

0.45 

20.00 

80.00 

0.20 

20.00 

50.00 

8.60 

25.00 

32.00 

40.00 

0.1)0 

0.25 


' 


\il 


\   ■ 


,-•" 

68 

ORGANIC 

Sodium  arscnnte. 

hiciirl>onate, 
"      borati', 
"      cnrbonntc, 
"      cbloratc, 
Sulphur, 
Strycliuia, 

"          nitrate, 
"          BUlpUnte, 
Urea. 
Vi'ratria, 
Zinc  chloride, 
"     Iodide. 
"     eulphatc. 

CIIKMISTUY. 

80.00 

8.00 

60.00 

SB.0O 

80.00 

0.10 

0.35 

4.00 

«.ito 

50.00 
1.00 
60.00 
40.00 
85.00 

"°*-W?gJ. 


so.oo 

8.00 
tiO.OO 
9S.00 
30.00 

0.10 

o.« 

1.00 

•i-i.ao 

M.OO 
1.00 
50.00 
40.00 
.3,V0O 


KTIIKR,S. 


61> 


ETHERS. 


.'^iMi'LK  i;tiii:es. 


Etliers  arc  products  l'onne<l  bv  the  action  of  alcohols 
upon  acids. 

JJy  iiiof^t  chcinist.s  tliey  aro  looked  upon  as  rctbrablc 

to  the  oxides  of  metals;  thus   £{J'  \  O  and  i^-JJ^  '    0 

may  be  re<^anlod  as  the  o.xides  resi)ectively  of  methyl 
and  ethyl.  They  bear  the  same  relation  to  alcohols 
that  oxides  of  the  metals  do  to  the  hydrates. 

Pota&sium  hydrate  KOH. 

Ethyl  hydrate,  or  ethyl  alcohol  O'.II-iOlI. 


Potassium  oxide 

Ethyl  oxide  or  ethyl  ether 


K) 


0. 


The  simple  ethers  aro  mostly  liquid.  They  are  very 
sliirjitly  soluble  in  water,  while  they  aro  readily  .soluble 
in  alcohol.  Ex])osed  to  the  action  of  alkali'no  solu- 
tions they  regenerate  alcohol. 

C4ll8().,+KIIO  =  C.,II«()+KC,II  O,. 


^M?I^WT~" 


' 


70 


oi:c;anic   ciikmistiiv 


ETllVL    KTIIEU. 


Synonyms :    Vinic  ether,  sulphuric  ether,  common  ether. 


(;   TT      O  —  ^2^^B  i  o 


Density  .730. 
Density  of  vapor,  37. 
Specific  gravity  of  vapor,  2.386. 
Boiling  point,  35.5o. 

To  prepare  this  compound,  sulphuric  acid  is  lieated 
with  alcohol  in  a  ri'tort,  placed  in  a  sand-Uath.  The 
ether  distills,  its  vapor  being  received  in  a  well  cooled 
condenser,  provided  with  a  long  tube  which  conthicts 
the  uneunder.sed  va])or  into  a  chimney. 

The  cork  adapted  to  the  tubulure  cf  the  letort  is 
provided  with  two  openings;  in  one  i.s  lixed  a  ther- 
mometer, through  the  other  a  tube  passes  which  fur- 
nishes the  eui)]ily  of  alcuhoL  All  the  connections 
should  close  perfectly.  When  the  apjiaratus  is  arranged 
in  this  manner,  pour  7^0  grams  of  S5  jx-rcent.  or  IH)  per 
cent,  alcohol  into  the  retort,  and  add,  little  by  little,  100 
grams  sid|)huric  acid  of  l.Slsp.  gr.,  then  heat.  When 
the  thermometer  attains  IHO",  cause  the  alcohol  to 
llow  from  the  upper  vessel  at  a  rule  sufticient  to  keep 
the  temperature  between  130°  aiul  1 10".  The  weight 
of  alcohol  capable  of  being  transformed  into  ether  is 
from  18  to  15  times  the  weight  of  the  mixture  first  in 
troduced  into  the  retort.     The  distilled  Ii(juid  is  mixed 


KTHKUS. 


'l 


ion  ether. 


cid  ifi  lieatcd 
-Uiitli.  The 
I  well  cooled 
ich  conducts 

;lie  letort  is 
ixed  a  tlier- 
!s  which  t'ur- 

coniicetioiis 
s  isai'i'aiii^cd 
lit.  or  yo  jjer 
l)y  little,  100 
leat.  When 
e  alcohol  to 
lent  to  keep 

The  weight 
into  ether  is 
;tiire  first  in 
|iiid  is  mixed 


with  1:>  parts,  to  every  100  of  its  weight,  of  a  solution 
of  soda  liaving  a  specific  gravity  of  1.32,  and  agitated 
from  time  to  time,  dm-ing  4S  hours. 

The  ether  is  decanted  hy  means  of  a  glass  siphon, 
redistilled  and  lour-hftlis  of  the  liipiid  C(.llected.  The 
remainder  may  serve  for  a  future  operation. 

This  furnishes  ordinary  etlier.  To  further  purifv, 
wash  with  water,  decant  aiul  treat  for  two  dayswith  equ'al 
])arts  of  quick  lime  and  fused  calcium  chloride.  Wil- 
liamscm  has  clearly  shown  that  etherification  takes 
l)hiee  in  two  stages  or  successive  reactions  as  follows: 

CAU  + 1  l^SO^  ==  ]  I,()  +  ^(^TI,)HS()4. 

EtliylBiilphuric  acid. 

(C JI,)ILS( ),  +  c,li,( )  _  c,H,o( )  +  H,S(),. 

This  explains  liow  a  small  quantity  of  sulphuric 
acid  etherizes  a  large  amount  of  aicohol,  since  sul- 
phuric acid  is  constantly  regenerated.  This  is  con- 
firmed hy  the  following  experiment.  Iodide  of  etlivl 
IS  made  to  react  upon  potassium  alcohol;  ether  \s 
ohtained  as  indicated  hy  the  reaction; 

CJIJ  -HC,I1,0K  ^  CMI,„0  +  KI. 

Ether  is  a  neutral,  volatile  li.piid,  colorless,  having  a 
hunung  taste  and  a  strong  agreeahle  odor.  When 
agitated  with  water  it  rises  to  the  surface,  hut  the 
water  dissolves  about  one  ninth  of  its  own  weight  of 
the  ether.     It   is  misciMe  with  alcohol  in  all  in-opor- 


^j 


72 


OliGANIO     CIIEMISTKY. 


I      I 
{      i 


tioiis  and  with  wood  spirit.  Ether  is  fre(|iieiit]y  udid- 
terated  witli  the  latter  Kubstaiiee.  Xext  to  alcohol  it 
is  the  most  generally  employed  solvent  for  organic 
substances.  It  dissolves  resin,  oils  and  most  com- 
pounds rich  in  carbon  and  hydrogen. 

Bromine;  iodine,  chloride  of  gold  and  corrosive  sub- 
limate are  soluble  in  this  li(piid.  It  dissolves  phos- 
])borus  and  sulphur  in  small  quantity. 

W.  Skey,  (S — Aug.  3, '  77,)  has  shown  that  contrary  to 
the  usual  statement  in  standard  works,  ether  dissolves 
uota])le  quantities  of  the  alkalies. 

At  a  red  heat  it  is  decom])osed  and  furnishes  carbon 
monoxide,  water,  nuirsh  gas  and  acetylene. 

It  is  exceedingly  inflammable,  and  burns  with  a 
bright  flame. 

Its  extreme  volatility,  the  density  of  its  vapor,  its 
insolubility  in  water  and  its  great  inflammability  render 
its  use  dangerous,  and  explosions  caused  by  it  are  of 
frequent  occurrcMice.  It  should  never  l)e  brought  near 
a  fire  or  light  in  open  vessels.  In  case  ether  inflames, 
it  is  best,  if  possible,  to  at  once  close  the  vessel  con- 
taining it,  and  thus  avoid  the  more  serious  conse- 
quences ensuing  from  an  explosion.  Exposed  to  the 
air  it  experiences  a  slow  combustion  as  in  the  c;5?e  of 
alcohol,  and  the  same  compounds  are  the  result. 

Chlorine  acts  violently  upon  it;  in  moderating  the 
action,  the  whole  or  a  ])art  of  the  hydrogen  may  be 
replaced  atom  for  atom  by  chlorine. 

Uses. — It  is  used  in  pharmacy  in  preparing  etherial 


ETHERS. 


73 


eiitly  udul- 

I  iik'ohi>l  it 

for  oi'ganic 

most  coin- 

•ro?ive  sub- 
olves  phos- 

contrary  to 
er  dissolves 

shes  carbon 

rns   with  a 

5  vapor,  its 
tility  render 
by  it  are  of 
rought  near 
er  inflames, 

vessel  con- 
•ious  coiise- 
osed  to  the 

the  c;!ve  of 
esult. 

leratiiig  the 
ijen  may  be 


inif  etherial 


tinctures,  and  as  an  antispasmodic  and  stimulant  in 
tlie  well-known  Hoffmann's  anodyne.  Its  most  iniiior- 
taiit  use  in  medicine  is  as  an  anesthetic,  than  which 
none  is  safer  or  more  reliable  in  efficient  hands.  It 
is  extensively  employed  in  the  laboratory  and  in 
photography. 

COMPOrXD    KTUEKS 

are  bodies  built  up  on  the  type  of  water,  having  one 
half  the  hydrogen  replaced  by  a  hydrocarbide  and  the 
other  half  by  a  comi)ound  radicle  containing  oxygen, 
or,  in  other  words,  by  the  radicle  of  an  acid. 


ACETIC  ETHER, 


(C^H,)     ) 

(C.HgO) 


O. 


To  prepare  this  ether  8  parts  of  very  concentrated 
alcohol  are  distilled  with  7  parts  of  sulphuric  acid  and 
10  parts  of  anhydrous  sodium  acetate,  which  may  be 
replaced  by  20  parts  of  dry  lead  acetate.  The  distil- 
late is  agitated  with  a  solution  vt'  calcium  chloride 
containing  milk  of  lime,  decanted,  dried  over  calcium 
chloride  and  finally  distilled. 

Seven  parts  of  water  dissolve  one  part  of  this  body. 
Alcohol  and  ether  dissolve  it  in  all  proportions.  It 
is  a  solvent  for  many  organic  bodies.  It  is  easily  de- 
composed on  contact  with  water.  Potassa  also  effects 
this  decomposition  very  readily.  A  pi-olonged  action  of 
ammonia  transforms  it  into  acetamide  and  alcohol. 


14 


OIUI.VNIC    CHEMISTRY. 


M  ill 


OXALIC    KTIIKRS. 

Oxalic  acul  beiii-  a  bi])asic  acul,  furnishes  with 
alcohol  two  combinations,  one  lacing  acul  =vu(l  c^M-able 
ofc.nibinin-  with  bases  ;  the  other  is  neutral,  C.;li,,<  >.• 

Onlv  the  latter  is  of  interest.  It  may  be  prepared 
by  introdncing  four  parts  of  i»0  per  cent,  alcohol  and 
four  parts  of  oxalic  acid  into  a  retort,  adding  to  tins 
n.ivture  three  to  six  parts  of  sulphuric  acid  and  then 
rapidly  distilling  ;  the  pr..duct  is  washe.l  several  tunes, 
dried/then  redistilled,  collecting  only  the  lupiid  whicii 
passes  over  at  1S4".  This  ether  is  aromatic,  ody,  and 
frraduallv  decomp(Jses  in  water. 
"  Potassium  changes  it  into  carbonic  ether. 

If  oxalic  ether  is  atjitated  with  ammoma,  a  white 
powder,  omnude,  and  ethyl  alcohol  are  produced. 

^^i  '.().,+N4n'== 
2^(c,n5)'.  (»)+nJ,  II.;  " 


(h: 


Oxamide  mav  be  considered  as  derived  from  two 
molecules  of  ammonia,  and  belongs  to  a  class  ot  bodies 

called  tZ/Vn/NV/t'S.  .        n        .  ^i 

It  i.  a  white  substance,  insoluble  m  cold  water  and 
alcolK  .1.  Heat>  'd  with  mercuric  oxide  it  is  transtormed 
into  carbon  dioxide  and  urea.     (Williamson.) 


ETHKRS. 


To 


iiishes  with 
lud  callable 
ral,  C,H,,( ),. 
be  prepared 
alcohol  and 
ding  to  this 
•id  and  then 
we  ral  times, 
liipiid  which 
tie,  oily,  tiud 

er. 

mia,  a  white 

)rodnced. 


ved  from  two 

class  of  bodies 

!old  water  and 
is  transformed 
ison.) 


Oxalic  ether  treated  with  ammonia  in  solntion  in 
alcohul  t'nrnishes  o,f<iiiitr  etlier. 

In  this  eoniiecti(jn  tlit;  eornpoiind  of  the  organic 
radicles  with  the  liah.id  elements  are  usually  studied: 
they  ar((  not  unfreijneiitly  denominated  ethers  of  ,ae 
hydracids.     Their   type    is   a   molecule  of 

hydrogen,  "  ' 


Hi 


(  UI.ORIDE  OI'  KTIIYf,  OR  CnLOKUYDRIC  ETUEB. 

C2H,CI=C,H-,  I 
'Clf 

This  body  is  formed  in  small  quantity  when  ethy- 
lene is  made  to  react  upon  hydrochhjric  acid. 

To  i)repare  it,  alcohol  contained  in  a  flask  sur- 
rounded by  cold  water,  is  saturated  with  hydrochloric 
acid  gas  and  the  mixture  then  distilled. 

C,H„0+HCl=C,H,CI+H.O. 

It  is  also  obtained  by  pouring  int.,  a  flask  contain- 
ing 2  paits  common  salt,  a  mixture  of  1  pait  alcohol, 
and  1  part  sulphuric  acid  :  it  h  then  gently  heated 
and  the  ether  collected  as  jireviously  shown. 

It  is  a  liquid  of  an  agreeable  odor,  and  very  volatile, 
having  a  boiling  point  of  li>°and  a  vapor  density  of 
<>4-.  A  red  heat  decomposes  it  into  ethylene  ami 
hydrochloric  acid  gas.  It  is  combustible  and  burns 
with  a  green,  smoky  Hame  ;  water  dissolves  the  fif- 
tieth j)artof  its  volume,  alcohol  dissolves  it  completely. 


MaiiiivMiiib 


76 


ORGANIC    CHEMISTUY. 


With  chlorine  it  furnij^hes  a  oomplete  and  regnlar 
series  of  products  of  substitution  whicli  an^  not  iden- 
tical, but  isonxeric  with  tlio  chlorine  products  of 
ethene. 

Their  forinulsB  are: 

C2H4CI2 
CoH.tCls 

C0H..CI4 
C,H  CI5 
C,  Cle. 

IODIDE   OF    ETUYL  OK    HYDUOIODIO    ETIIEK. 


aii,i  =  ^^'^  \ , 


is  obtained  on  causing  alcohol  to  react  ui)ou  iodide  of 
phosphorus;  the  action  is  violent  with  white  phos- 
phorus, considerably  less  so  with  red  pliosphorus. 

Six  hundred  grams  of  concentrated  alcohol  are  intro- 
duced into  a  retort  witli  140  grains  of  amorphous 
phosphorus,  and  to  this  mixture  450  grams  of  iodine 
are  added.  The  distilling  is  carried  nearly  to  dryness. 
The  product,  condensed  in  the  receiver,  is  washed  with 
water  containing  a  little  potassa ;  afterwards  with  pure 
water.  It  is  then  dried  over  calcium  chloride  and 
again  distilled. 

Iodide  of  ethyl  is  a  colorless  liquid  Its  density  is 
1.975.  It  becomes  colored  on  exposure  to  light,  being 
slightly  decomposed  ;  it  is  again  rendered  colorless  on 
agitating  it  with  an  alkaline  solution,  which  absorbs  the 


ETHERS. 


77 


iind  regnlar 
in^  iu)t  iden- 
products   of 


rniEK. 


pou  iodide  of 
white  phos- 
sphorus. 
•liol  areintro- 
f  amorphous 
iins  of  iodine 
ly  to  dryness. 
;  washed  with 
rds  witli  pure 
chloride  and 

[ts  density  is 
;o  light,  being 
1  colorless  on 
ch  absorbs  the 


acid  formed.  Itl)urns  with  a  green  flame,  leaving  a  resi- 
due of  iodine.  Ammouiuni  eoni]»ounds  in  alcoholic,  or 
a.pieous  solution,  furnish  ethylaniine.  This  amine  can 
he  attacked  in  its  turn  by  iodide  of  ethyl  and  yields 
dietliylaniiiie  and  oxide  of  tetrethylaunnonium.  The 
knowledge  of  these  reactions  and  their  api^lication  to 
other  iodides  are  the  basis  of  a  general  mode  for  the 
preparation  of  oi-gunic  ba.-es  originated  by  Ilotihiann. 
Iodide  of  etliyl,  unlike  tlio  chloride,  is  readily  decom- 
jtuscd  by  solutions  of  silver  nitrate,  giving  a  precipi- 
tate of  silver  iodide. 

CJI,I  + AgXO,  =  (C,ir,0  XO;,  +  AgL 

Ci-AXIDK  or  Ellivr.,  OIJ  CVANUYDRIC  ETHEK. 

This  ether  is  obtained  on  distilling  in  an  oil-bath 
1  })nrt  of  potassmm  cyanide,  with  1-5  part  of  an  alkaline 
suipho-vinute.  To  the  product,  redistilled  in  a  bath  of 
salt-water,  nitric  acid  is  slowly  added  in  excess  ;  it  is 
then  subjected  to  another  distillation.  Finally,  it  is 
dried  over  calcium  chloi-ide,  and  that  which  passes'  over 
trora  195°  to  200"  is  collected  on  redistillation. 

Cyanide  of  ethyl  is  a  colorless  liquid  of  an  alliaceous 
odor,  boiling  at  Jt7". 

Cyanide  of  ethyl  is  decomposed  by  potassium  hy- 
drate; ammonia  is  produced,  and  the  acid  obtained 
corresponds  with  a  higher  homologous  alcohol. 


J 


I 


78  ORGANIC     CHEMISTRY. 

CN(C,II5)  +  2II,0-- NIl:,  +  ( -ilUV 

Propionic  iicid. 

M.  Meyer  obsen^ed  some  years  ago,  that  if  cyanide 
of  silver  is  treated  with  iodide  of  etliyl,  a  lii^iiid  is 
forniod,  boiling  at  82",  of  an  odor  which  is  not  that  ot 
ordinary  cyanh}  k  ■  "ic  ether.  Gautier  has  shown  that  this 
is  an  isomeric  body,  and  that  there  are  two  isomeric 
series  of  cyanhydric  ethers.  Hoffmann  has  given  a  dis- 
tinctive character  to  these  bodies:  under  the  intiuence 
of  the  alkalies  they  jiroduee  a  ti\ed  substance,  but 
this  is  formic  acid  and  not  ammonia,  and  a  volatile 
substance  which  is  a  compound  ammonia. 

CN(C,II5)+2IL()=CII,(),  +  C,II;,    \  N. 

^  '     .-^- —      II  ) 

Formic  acid.       Ethylamiue. 

OeOxVNO-metalt.ic  Compounds. 

Iodide  of  ethyl  attacks  the  metals  and  furnibl.-s  a 
class  of  bodies  called  organo-metalliG  radicles.  None 
of  these  bodies  are  found  in  nature.  They  are  formed 
from  the  iodohydric  ethers  by  the  substitution  of  a 
metal  for  the  iodine: 

Zn  +  2(C,1I,I)  -  (CoIl5),Zn  +  Znl,, 

2Sn  4-  2(C,Il5l)  -  (CJIO^Sn  +  SnI,. 

Practically  these  metallic  radicles  are  obtained  by 
various  reactions: 


ORGANO-METALLIC  COMPOUNDS. 


79 


ttcid. 

hut  if  cyanide 
yl,  ii  li(|iiicl   is 

is  TU)t  that  ot 
howu  that  this 

two  isomeric 
ii\s  given  a  dis- 

the  inrtuence 
substance,  but 
and  a  volatile 
ii. 

N. 

lue. 
:)8. 

nd  furnibl.'-s  a 
iidicles.  None 
liey  are  formed 
bstitntion  of  a 


Znl,, 

-Snij. 

ire  obtained  by 


1.  J'.y  the  action  of  the  metal  upon  the  iodide,  for 
example; 

2C,TIJ  +  Zn=(C,Ilg).,Zn  +  Znl,. 

In  certain  cases,  with  tin  for  instance,  the  reaction  is 
not  as  distinct,  and  there  is  formed  in  addition  tostan- 
netliyl  iodide,  staunethyl  iodides  variously  condensed. 

2d.  The  metal  is  treated  with  another  radicle;  thus 
sodium-ethyl  is  prepared  by  the  action  of  sodium 
upon  zinc  ethyl, 

(CJI,)oZn  f  Xa,=Zn  +  2C JI,Xa. 

3d.  On  d(;com[)usin<f  a  metalloid  compound  radicle 
with  a  metallic,  chloride, 

;jZii(  '1,  +  (C  ,n,>,P=3(C,lI,)Zn  +  2PCI3. 

ith,  Stannethyl  is  obtained  by  plunging  a  plate 
of  zinc  into  a  soluble  salt  of  this  radicle:  the  radicle 
is  precijntated  in  the  form  of  an  oily  licpiid. 

Cacodyl,  As(Cir;j)2  was  the  first  discovered  of  thisclass 
of  bodies.  It  was  obtained  by  Buiisen  on  distilling 
arsenous  acid  with  potassium  nitrate.  The  organic 
radicles  combine  with  mf-talloids  with  more  or  less 
energy  ;  zinc-ethyl  and  cacodyl  take  fire  in  the  air  • 
they  also  decompose  water.  The  products  of  oxida- 
tion vary  witlithe  luiture  of  the  compounds  employed; 
zinc-ethyl  furnishes  the  Ixidy,  CJi/uO,  ziuc-ethyl- 
atc,  M'hich,  in  coutact  with  water,  jiroduces  alcohol  and 
oxide  of  zinc.     The  metals  wliich  are,  le»s  readily  oxy- 


80 


ORGANIC    CHEMISTRY. 


S  H 


dized,  such  as  tin,  lead  and  mercury,  give  oxides 
which  play  tho  parts  of  bases,  and  these  latter  com- 
port themselves  like  the  oxides  of  the  metals  they  con- 
tain. Finally,  the  radicles  formed  by  the  elements, 
phosphorus,  arsenic,  and  antimony,  give,  with  oxy- 
gen, compounds  which  generally  have  the  character  of 
acids. 

Some  of  the  organic  derivatives  containing  phos- 
phorus are  very  complex.  For  instance,  J.  Auanolf 
(00-' 75-493)  has  obtained  a  body  he  denominates, 
methyldiethyJphosphoniumpliemjloxidehjdmte! 

To  prepare  zinc-ethyl^  Ave  introduce  into  a  flask 
connected  with  a  condenser  inclined  in  sneh  a  manner 
that  the  vapors  find  their  way  back  into  tho  flask,  100 
grains  iodide  of  ethyl,  75  grams  of  zinc,  and  6  to  7 
grams  of  an  alloy  of  zinc  and  sodium,  and  heat  in 
the  water  bath  until  the  zinc  is  dissolved ;  then  the 
condenser  is  incliiR'd  as  usual,  and  tho  distilling  is 
eflFected  over  a  direct  Are,  collecting  the  liquid  pro- 
duct  in  a  flask  "illed  with  dry  carbon  dioxide. 
Finallv  it  is  again  distilled  in  this  gas,  and  that  col- 
lected'which  passes  over  from  116"  to  120^  All  the 
vessels  and  all  the  substances  should  bo  absolutely 
dry,  and  it  should  always  be  collected  and  distilled  m 
mcvA^,  or  in  carbon  dioxide.  It  is  a  colorless  liquid, 
whose  density  is  1.182,  boiling  at  118°,  inflammable 
on  exposure  to  the  air. 

With  sodium  this  body  furnishes  sodium-ethyl,  and 
with  chloi-ide  of  phosijhorus  or  arsenic,  it  furnishes 
triethyl  phosphine,  P(C..Il5)3,  an^l  trietliyl  arsine, 
As  {6^\^^. 


ETHERS. 


81 


give  oxides 
!  latter  coin- 
;al8  they  con- 
lie  elementR, 
!,  with  oxy- 
)  character  of 

ainiiifj  ph68- 
e,  J.  Auaiuift' 
lenoiuiuates, 
yd  rate! 

into  a  flask 
leh  a  manner 
;lio  flask,  100 
,  and  6  to  7 

and  heat  in 
ed ;  then  the 

distilling  is 
e  liquid  pro- 
)on  dioxide, 
and  that  col- 
20".  All  the 
>o  absolutely 
,d  distilled  in 
lorless  liquid, 

inflammable 

um-ethyl,  and 
!,  it  furnishes 
etliyl    arsine, 


Mercury-methyl,  treated  with  iodine,  furnishes  a 
liydrocarbide  which  has  the  formula  ot  methyl,  Clia. 

Professors  Crafts  and  Iw-iedel  (T2-['i]19-33-l)  have 
prepared  a  large  number  of  comixuiiuls  of  silicon  with 
compound  radicles,  from  which  they  have  deduced 
valuable  theoretical  considerations. 

MISCELLANEOUS  ETHERS. 

Formic,  butyric,  valerianic  ether,  and  other  ethers 
of  the  tatty  series  are  prepared  in  the  same  manner  as 
acetic  ether,  and  liavo  the  general  properties  of  this 
ether.  The  odor  of  these  ethers  is  agreeai)Ie.  Bu- 
tyric ether  has  the  odor  of  ]Mne-apple,  and  \alerianic 
ether  that  of  ])par>  ;  (cnanthylic  ether  has  tha  aroma 
of  wine,  etc.  They  are  used  in  the  nianufaetiire  of 
syrups,  flavoring  extracts,  and  for  imparting  an  odor 
to  liquors. 

If  the  difference  between  the  points  of  ebullition  of 
these  ethers  is  examined  it  will  he  seen  that  the 
addition  of  the  elements  (.^ir^  causes  an  elevation  of 
about  20"  in  tlie  point  of  ehullition.  Kopp  hns 
shown  that  this  fact  is  a  general  one  and  applies 
to  the  alcohols,  and  aeids  of  the  same  series,  and  to 
the  homologous  bodies  in  genei-al. 

Point  of  ebullition. 

-       55" 

74" 

95" 

-       119" 

133" 


Formic    ether, 
Acetic         " 
Propioidc   " 
Butyric      " 
Valerianic  " 


Difterence. 

19" 

2P 

14" 


i<rit 


MiHita 


1| 


' 


82 


OKOANIC     CIIKMISTHV. 


The  ])oiling  point  of  one  of  these  hocUes  luay  accord- 
iuglj  be  predicted,  if  that  of  one  of  its  homologous 
substances  is  known.  There  is  a  certain  close  relation 
betweeti  the  point  of  el)ullition  of  an  ether  and  that 
of  the  acid  wliose  radicle  it  contains: 


Point 

of  ebullition. 

Difference 

Formic  acid, 
'<       ether. 

- 

105°  ) 
55"  f 

50° 

Acetic  acid 
•'      ether, 

- 

11S"| 

44° 

Propionic  acid, 
"       ether,     - 

- 

1 40°  1 
tt5°  \ 

4.5° 

Butyric  acid, 
'"'       ether,    - 

. 

163°  ] 
ll{t°^'       . 

44° 

The  solubility  in  water  of  the  ether  formed  by 
homologous  acids  varies  with  the  molecular  weight  ; 
thus  formic  ether  is  quite  soluble,  acetic  ether  is  less 
stjluble,  butyric  ether  is  but  laightly  so,  and  valerianic 
ether,  whicli  follows  it,  i:.  nearly  insoluble. 

MERCAPTANS    AND    IIIKIK    KfUERS. 

On  substituting  Bulphur,  selenium,  or  tellurium  for 
oxygen  in  the  alcohols  of  ditierent  atomicity.  suli)lmr, 
selenium,  or  tellurium  alcohols  are  obtained,  whicli 
are  designated  as  mercaptans,  selenium  mercaptans, 
and  tellurium  mercaptans;. 

Ethers  proi)er  correspond  to  these  as  to  ordinary  al- 
cohols.    These  ethers  are  derived  either  by  the  substi- 


iiiay  accord- 

hoinologous 

jluse  relation 

ler  ami  that 


Difference. 
5U° 
44° 
45° 
44° 

formed  by 
idar  weight ; 
ether  is  less 
Lud  valerianic 
e. 

f.S. 

tellurium  for 
city.  Buljilmr, 
talncd,  which 
L  niercaptans, 

o  ordinary  al- 
by  the  substi  ■ 


ETHERS. 


83 


tntion  of  an  alcohol  radicle  for  the  typical  hydrogen, 
as  hai)peiis  with  nionatoniic  mercaptans,  or  by  the 
elimination  >A'  II^S,  as  is  the  case  with  biatomic  mer- 
captaii.s. 

One  only  of  each  of  these  two  classes  will  be  alluded 
to  here. 

Ethyl  sulphide,  or  hydrosulphu-  )  .,  ..  C.TI,  )  ^ 

ric  ether,  ( *-i^^iot? ""  (j  jj.'  .■  S. 

Ethyl  mercaptan,  C4H6S=^^-'f|'  !-  S 

41   ) 

To  iirepai-e  the  sulphide  a  cuiTent  of  ethyl  chloride, 
is  passed  into  an  alcoholic  solution  of  potassium 
sulphide. 

The  mercaptan  is  prepared  by  the  action  of  potass- 
ium hydro-sulphide  or  ethyl  sulphide. 

In  either  case  potassium  chloride  is  formed. 

K,S  +02H,ri=C,H,oS  +  2KCl 
KilS  +  C.HsCl   =C,H6S  +  K('l. 

These  bodies  are  afterwards  separated  by  distiilation- 
Like  all  the  sulphur  derivatives  of  alcohol,  they  have  a 
nauseous  odor.  The  sulphide  boils  at  91«  the  mer- 
captan at  36°. 

JnXED    KTHKKS 

containing  two  different  radicles,  are  obtained  by  act- 


.r     1'' 


:^ 


II 

-'Si 


m 


]^^tj^lr.i^j.^k.:Afi^t'^?i.  ■ 


m    t 


^-f^s  m 


■  I' 
•ii' 

"lit 


It*,. 

H;li 


! 


84 


ORGAl^IO    CHEMISTRY, 


ing,  for  instance,  with  ethyl  iodide  upon  potassium 
niethylate,  thus : 

ethyl  iodide,    potassium     potaseinm  methyl-ethyl 
methylate.         iodide.  etlier. 

or  by  acting  on  hydric  methyl  sulphate    '  jj'  ^  SO^ 

with  ethyl  alcohol.  The  following  is  a  list  of  sume  of 
the  moi'e  important  mixed  ethers  of  the  niouiitomic 
series; 


TABLE  OF   MIX1;D  ETHERS. 


UOILING   POINT. 


Methyl-ethyl  ether  C41sO=  ^JJ'  J-  ^^         + 1^° 


Methyl 


ayl-amyletlierCrJInO-cH    ^^  ^^^ 


Ethyl-butyl  ether  C6Hi40=  ^^^^  I  O 


80" 


Ethyl-amyl  ether   C:H,«()  =  q^  [  O  113« 

Ethyl-hexyl  ether  Csll;sO  =  g^^^  |-  O         132- 


>ii  potassium 

thyl 

II     \^* 

ist  of  some  of 
le  moiiiitoHiic 

UOILIXG   POINT. 

+11° 

92" 

D         112° 
'J         132" 


ALDEHYDS. 


85 


ALDEHYDS. 

The  following  are  the  principal  aldehyde,  arranged 


in  series 


Formic  aldehyd 
Ethylir*.  aldehyd 
Propylic  aldehyd    - 
Butylic  aldeiiyd   - 
Valeric  aldehyd 
(Enanthylic  aldehyd      - 
Caprylic  aldehyd    - 
Caproic  aldehyd 
liutic  aldehyd 
Ethalic  aldehyd 

AUylic  aldehyd  (acrolein) 


G  HjO 
C,H,0 

CsTIeO 

C4H80 
C5H.0O 

CJ1„0 
CsIIibO 
C,oH,oO 

c„ii,>o 


C3  H,0 


cji,„.,o. 

Campholic  aldehyd   (camphor)  CioH.fiO 


se 


ORGANIC    CUEMISTUY. 


;        < 


CJI 


3n-8 


p. 


Benzoic  aldehyd  {oil  of  hitter  almonds)  Q-,  II«  O 
Toluic  aklehyd  -  -  -  -  CgllsO 
Cuininic  aldehyd  ...        -  CioH,.0 

Svcocervlic  aldehyd         -        -        -       CisUsO 


CellsO. 


Cinnamic  aldehyd  {oil  of  cinnamon) 

Aldehyds  may  be  regarded  as  bodies  built  upon  the 
type  of  one  or  more  molecules  of  hydrogen,  in  which 
one  half  the  hydrogen  atoms  are  replaced  by  one  or 
more  molecules  of  an  oxidized  carbohydride. 

The  formation  of  aldehyd,  (aZcohol  <^/A,?/(/rogenated), 
may  be  illustrated  by  the  following  equation : 

CoHcO-H.,  =  C2H4O 


Ethyl  alcohol. 


Ethyl  aldehyd. 


Aldehyds  are  obtained  by  the  oxydation  of  alcohols, 
but  thoy  are  only  the  first  products  of  oxydation.  They 
are  capableof  combining  with  an  additional  molecule  of 
oxygen,  forming  acids;  hence  the  aldehyds  are  inter- 
mediiito  between  alcohols  and  iK'ids. 

ORDINARY    ALDEHYD. 

c,n40=c,n:,o ) . 

in 

This  substance  is  formed  by  the  slow  oxydation  of 
alcohol.  • 


CJI«0 

Cs lis  O 
C,oTi,.0 
CsII^O 


CellsO. 

t  upon  the 
I,  in  which 
by  one  or 
e. 

rogenated), 
ii: 


of  alcohols, 
ition.  They 
molecule  of 
Is  are  iiitev- 


oxydation  of 


••"?»- 


ALDEIIYDS. 


87 


Alcohol  is  treated  with  a  mixture  of  manganese 
hinoxide,  or  of  potassium  bichronuxte,  and  sulphuric 
acid,  and  distilled,  care  being  taken  to  keep  the  re- 
ceiver well    cooled.     Besides   aldehyd,   acetyl,   acetic 
ether,  acetic  acid  and  water  are  formed.     The  product 
is  again  distilled,  care  being  taken  to  collect  only  that 
portion  M'liich  passes  over  above  60".     This  liquid  is 
mixed  with  ether,   and,  when  cool,   a  stream  of  drv 
ammonia  gas  is  caused  to  i>ass  through  the  solution". 
Crystals     of     ammonium      aldehyd     are      formed, 
C.Il3(XIl4)0,  which  are   decomposed    by  dilute  sul- 
phuric acid.     The  mixture  is  then  distilled. 

Aldehyd  is  a  colorless,  very  volatile  liquid.  It  is 
soluble  in  water,  alcohol  and  ether,  and  possesses  a 
strong,  somewhat  stifling  odor. 

The  salient  property  of  aldehyd  is  its  avidity  for 
oxygen.  If  a  few  drops  are  poured  into  water  the 
latter  becomes  acid;  it  is  therefore  a  valuable  reduc- 


ing agent. 


If  aldehyd,  or  ammonium  aldehyd,  ^\14!  I    is 

•^  jN  II,  f  , 

poured  into  an  ammoniacal  solution  of  silver  nitrate, 
on  slightly  elevating  the  temijerature,  metallic  silver  is 
deposited.  This  silver  adheres  to  the  sidesof  the  tube, 
and  covei-s  it  with  a  mirror-like  coating.  This  prop- 
erty is  the  basis  of  a  process  of  silvering  glass  globes 
and  other  hollow  articles  of  glass. 

Aldehyd  is  attacked  by  chlorine  and  bromine,  and 
furnishes,  by  substitution,   various  products,  of  which 

Chlokal   CJICI3O,  is  the  most  important.     J5y. 


^^1 


■^=^"ati»^*paa^ji>wT*f«Ki"tMaai^Uiiai'l^aajaiay* 


m 


ORGANIC    CHEMISTRY. 


dm  to  ofchlomU  or  C,IlCl/)  +  lI>0.1iasbeen  prepared 
now  for  several  years  in  very  large  (juantities,  for 
medicinal  purposes.  Its  name  is  derived  from  chlor- 
ine  a^Icohol. 

Absolute  alcohol  is  saturated,  first  cold,  then  hot, 
with  dry  chlorine.  The  litpiid  obtained  is  mixed  with 
its  volume  of  concei  '  ated  sulphuric  acid.  The 
supernatant  liquid  is  decanted,  and  distilled  in  an 
earthern  retort,  with  one-fourth  its  weight  of  sulphuric 
acid.  The  anhydrous  chloral  obtained  is  redistilled 
twice  with  calcium  carbonate  aiul  7  to  8  per  cent,  of 
water.  The  hvdrate  is  then  obtained  in  handsome 
crystals,  CJICUO  +  II.O,  soluble  in  water.  It  has 
been  known  for  some  time  that  this  body  is  decom- 
posed in  presence  of  alkalies  or  alkaline  carbonates, 
into  cliloroform  and  formic  acid, 

CJICl30  +  H,0  +  KI10=KCHO,  +  CIICl3+IIA 

Potassium    Chloroform, 
formiate. 

Tlie  question  appeared  ])ertinent  whether  a  similar 
transformation  would  be  affected  in  the  human  body, 
under  the  action  of  the  alkaline  fluids  there  present, 
notably  those  of  the  blood,  and  thus  develop  chloro- 
form. 

Liebreich  was  the  first  to  administer  chloral,  and  he 
at  once  obtained  the  anesthetic  efteeta  of  chlorotorm. 
His  oxperiiiients  were  repeated  in  difterent  countries, 
and  hydrate  of  chloral  soon  came  into  general  use  as 
a  hyponotic. 


ALDEHYDS 


89 


n  prepared 
ntities,  for 
from  chlor- 

,  then  hot,  ' 
mixed  with 
icid.  The  I 
illed  in  an 
)t'  sulphuric 
redistilled 
per  cent,  of 
I  handsome 
er.  It  has 
y  is  decern- 
carbonates, 


Dla  +  II^O. 

•form. 


Chloral  lijdrate  fur  medical  use  must  he  crystalline 
and  possess  the  following  properties:  it  should  be  col- 
orless, traiis])arent,  and  have  an  aromatic  odor,  a  caus- 
tic taste,  readily  soluble  in  water  without  furnishing 
drops  of  oil,  also  soluble  in  alcohol,  c'lior  n  ',tJuC 
benzol,  and  earbon  bisulphide;  it  should  \v  r  5ijo  to 
58",  solidify  at  about  15",  boil  and  volatilize  Vtify 

at  95".     With  caustic  potassa it  should  fun  lo- 

form,  and  with  sulphuric  acid,  chloral,  withoiu  ..ocoui- 
iiig  brown.  Its  aqueous  solution  should  be  neutral 
and  not  jiroduce  any  turbidity  with  silver  nitrate  and 
lutr.c  acid.  E.xposed  to  the  air  it  shorld  not  become 
moist.  Accordingtorecentinvostigationsbyliebreich, 
[fiO-69-673)  chloral  produces  the  opposite  phvsiolo<rl 
>cal  etlects  of  Btryclmine,  hence,  these  bodies  ma'y 
be  used  as  antidotes  one  for  the  other 

TI.e  remaining  aldehyds  are  not  sufficiently  im- 
portant  for  a  work  of  this  scope.  Camphor  has  al- 
ready  been  considered  in  connection  with  turpentine 


iv  a  similar 
umau  body, 
lere  present, 
^elop  chloro- 

loral,  and  he 
■  chlorotorin. 
Mit  countries, 
nieral  use  as 


..»  A.Ja,M^.^^'^^^^^ 


OliGANIO    CHEMISTRY. 


ORGANIC  ACIDS. 

ACIDS  CONTAININ'i  TWO  ATOMS  OF  OXYGEN. 


FATTY   ACID   8KRIKS. 


Formic 

acid, 

Acetic 

(( 

Propionic 

;( 

Butyric 

u 

Valeric 

(k 

Caproic 

i( 

CEnanthj  , 

»     ' 

Capryli" 

■.i 

Peli.ijonic 

a 

Capno 

ii 

Laurie 

(( 

Cocci  nic 

u 

Myristic 

u 

Palmitic 

(( 

Margaric 

a 

Stearic 

a 

Arachidic 

ti 

Cerotic 

a 

Melissic 

u 

c„n,„o,. 


C  H,0, 
C,H4  0, 
CsHeO, 
C4II8O, 

CjIIioO, 

-  cji,A 

C,IIuO, 
CsHkO, 
CJLsOj 

CioIIaoOj 

c,,n^o, 

CialljeOj 

CyHjsOa 

CieHj^Oi 

Ci:H3,0, 

CisHso^a 

-   C'^II^O, 

030x16002. 


nu-U.di.'.nii,imMM""iiiji" 


-r-l 


':ii,-ii.^i:'.'.-'^-,fW--^ 


-".  -y^=*-^??*-T';r^^-"-2v?p*.'?  i?^^^^:'fT:}:- " 


^^p'rtts^.rs'  rr,'n!^l 


r 


IMAGE  EVALUATION 
TEST  TARGET  (MT-3) 


^/     '4^4^ 


:/j 


fell 


^ 


V^ 


r 


'-m^  ■  ^J 


^j^ 


150    "^^      IfflIBB 


Photographic 

Sciences 

Corporation 


23  WEST  MAIN  STREET 

WEBSTER,  N.Y.  MStO 

(716)  872-4503 


CIHM/ICMH 

Microfiche 

Series. 


CIHM/ICMH 
Collection  de 
microfiches. 


Canadian  Institute  for  Historical  IVIicroreproductlons  /  Instltut  Canadian  de  microreproductlons  historiques 


I^Wi 


ORGANIC   AOIDS. 


91 


Acrylic  acid 
Crotouio  " 
Angelic  " 

Pyroterebic  " 
Campholic     " 
Moringic       " 
Physetoleic  " 
Oleic  " 

Doeglic        " 
Erucic  " 


c„ii,„_,o,. 


CnHin-^iOj. 


Soi'bic   acid 
Campliiu  " 


C  H^Oj 
C4ll«0,, 

Cg  H10O2 

CwHaoOa' 
C18H34O3 
CiaHagOa 
CaH^aOjj. 


Cg  Hg  O2 
CioHijOg 


ABOMATIO  ACID  8EBIE8. 


CnHan-sO^. 


Benzoic  acid 
Toluic      « 
Xylic       " 
Cuinic      " 
Alpha-cymio  acid 


'-^ntlan— loOji 


Giimamic  acid 
Pinic  " 


OTHgOa 
CgHgO, 

C9  HiqO, 

OioHijO, 

CiiHhOj. 


CsHgO, 
CjjoHaoOj. 


:.ji«i<'iM  iriMimkiiiiini^itm 


B 


■ 


n 


02  OROANIO    CHKMI8TBY. 


ACIDS  CONTAININa  THKKE  ATOMS  OF  OXYGEN. 


C„H,„0: 


nii^uv^s. 


Carbonic  acid 

Glycolic  " 

Lactic  " 

.Oxybutyric  " 

Oxyvaleric  '' 

Leucic  " 

(Enanthic  " 


CnH2n_3V-)3. 


Pyruvic        acid 
Scaminonic    " 
Kicinoleic      " 


CnHjn— it's- 

Gnaiacic       acid 
Lichenstearic  "     - 

Pyromeconic  acid 

CnH-in-sOa. 

Salicylic     acid    ■ 
Anisic         " 
Phloietic      ♦'    - 
Oxycnminic  " 
Thyinotic     "    - 


C  HjOs 
CaHiOs 
CsHcO, 
C^HsOs 
Cj  HjoOg 

Ce  H,,Ob 


C8H4O3 

CigHajOs. 


Cg  Hg  Oi 
C9  HuOs* 


CBH4O8. 


C,H,03 

C9H:oO, 

C„H,A 
CnHiA. 


■m 


re  EN. 


ItoO, 


l4  03 


E4O8. 


H,03 

H:oO, 
EI„Os. 


ORGANIC   ACIDS. 

Coumaric  acid     -        -        -      C9H8O3. 

ACID8  CONTAININO-  FOUR   ATOMS  OF  OXYGEN. 


98 


Glyceric  acid 

CnH^-aO. 

CsH^O,. 

Oxalic 

acid 

C,H,0, 

Malonic 

(( 

CsH4  04 

Succinic 

« 

C4H,04 

Pyro  tartaric 

{( 

C5H8O4 

Adipic 

(( 

C0H..0O4 

Pimelio 

K 

C7  HijOj 

Suberic 

U 

CJI„04 

Anchoio 

U 

C9  HuO, 

Sebic 

U 

C10HJ8O4 

Roccellic 

CnH2„_404. 

C„H„04. 

Fumaric 

acid 

C4H4O4 

Citraconic 

i( 

C,Ii«04 

Terebic 

(( 

CtH,„04 

Camphoric 

(( 

C,„H„04 

Lithofellic 

(( 

C»Ha.04. 

aai^L)iS!.saiMagaiaaeaKaa^,!ii» 


94 


ORGANIC    CHEMISTRY. 

CnHto-aOj. 

MelHtic 
Terechrysic 

acid 

C4Ha04 
CellsO^. 

CnH2n_804. 

Veratric  acid 

CiiH2n_ioO. 

C9H10O4. 

Phtalic 

Insolinic 

Choloidic 

acid 

C8H«04 

C9H804 

C«IIa804. 

- 

CnUjn— uO' 

Oxynaphthalic  acid 
Piperic                " 

CJT6O4 
Cj2H,o04. 

AOTTd  OONTAININO    5,    6,     7     AND     8     A  :OMS  OF  OXYGEN. 


Tartronic  acid 
Malic           " 

C3H4O, 
C4HeO,. 

C„II.,u-405. 

t 

Mesoxalic  acid 

CsHjOfl. 

CnHo„_«05. 

I604. 


10' 


,04. 


BO4 

38^4' 


,04 
I0O4. 


IF  OXYGEN. 


4O, 


A. 


ORGANIC    ACIDS. 

Cholesteric  acid 


95 


Crocoiiio 
Comenio 
Gallic 
Cholalic 


acid 


u 
u 


C'nH2n_208. 


Tartaric  acid 
Quinic        " 


V-'ntlon— I^'r 


Carballylic  acid 


Aconitic  acid 


Chelidonic 


Meconic 

Citric 
Mncic 


CnHin-eOa. 
CnHjn-ioOg. 

acid 

^nHiin-ioOt* 

acid 
(( 


CsHioOs. 


C5  Hj  O5 
Ce  11,05 
CJIeO, 

Ca4H4o05. 


C4H606 


CfcHttOe. 
C,H4  0e 

C,H4  0, 

CeHnO, 

CfiHioOs. 


Org  anio  acids  are  bodies  built  upon  the  type  of  one 
or  more  molecxiles  of  water,  hiving  one  half  the  hy- 
drogen replaced  by  an  organic  compound  radicle  con- 


9e 


ORGANIC     CHEMISTRY. 


taining  oxygen.  There  are  some  acids  whose  compo- 
sition is  not  definitely  fixed.  We  shall  first  examine 
the  monatomic  acids,  and  study  the  other  series  in  the 
order  of  their  atomicity. 

The  organic  acids  possess  tlie  general  properties  of 
the  mineral  acids.  Many  among  them,  like  aceticacid, 
have  a  very  decided  action  upon  litmus.  Generally, 
they  are  solid  and  crystallizable;  however,  formic,  pro^ 
pionic,  butyric  acids,  etc.,  are  liquid.  Acids  whose 
molecules  are  comparatively  simple,  are  oi-dinarily  sol- 
uble in  water— the  others  are  little,  or  not  at  all,  soluble 
in  this  solvent.  The  monobasic  acids  are  volatile,  at 
least  where  their  molecules  are  not  very  complex.  The 
polybasic  acids  are  decomposed  by  heat.  Their  salts 
are  ordinarily  crystallizable. 

METHODS  OF  PREPARATION. 

I.  The  acids  of  the  so-called  fatty  series  are  ob- 
tained by  the  oxidation  of  the  corresponding  alcohol, 
or  aldehyd,  which  latter  is  the  first  product  of  oxida- 
tion of  the  respective  alcohol. 

CjHeO -f- 02=C2H4O  4- II2O. 

V , < 

Acetic  aldehyd. 
C2H4O-f-Oj=C2H40,. 


Acetic  acid. 


II.  These  acids  are  also  produced  by  the  action  of 
alkalies  upon  the  cyanide  of  the  radicle  appertaining 
to  the  homologous  inferior  alcoliol. 


)se  compo- 
it  examine 
jries  in  the 

x>pertie8  of 
acetic  acid, 
Generally, 
armic,  pro- 
sids  whose 
inarily  sol- 
all,  soluble 
(volatile,  at 
)lex.  The 
Their  salts 


es  are  ob- 

ff  alcohol, 

of  oxida- 


action  of 
)ertaining 


ORGANIC    ACIDS.  97 

(CH3)CN  +  KIIO  +  HaO^^NHs + KCaHaOj 

Methyl  cyauide. 


PotagBium  acetate. 


III.  Acids  are  likewise  formed  by  the  union  of  the 
■elements  of  carbon  monoxide  and  carbon  dioxide  with 
hydrogen  carbides  and  water.  The  remarkable  syn- 
thesis of  formic  acid  by  Berthelot  is,  according  to  this 
method : 


C0-f-IL0=CH20 


2^2- 


Pelouze  has  shown  that  heat,  cnrefiilly  applied  to 
polyatomic  acids,  causes  them  to  part  with  a  certain 
number  of  molecules  of  water,  of  carbon  dioxide,  or  of 
both,  and  famishes  acids  more  simple  and  of  a  lower 
equivalence,  which  he  designates  by  the  name  oipyro- 
acids. 

2C4HeOe=C,,H804  -\-  2HjO  -f-  SCO., . 


Tartaric  acid.  Pyro-tartaric  acid. 

Of  all  the  series  of  acids,  the  most  numerous  and  the 
most  important  are  those  of  the  so-called  fatty  series- 
We  shall  presently  indicate  the  methods  by  which  they 
are  obtained. 

Tneir  boiling  point  increases  from  16"  to  20°  with 
each  addition  of  Cllj  to  their  molecule.  Certain  of 
their  salts,  those  of  calcium,  for  instance,  are  decom- 
posed by  heat,  furnishing  compounds  called  acetones. 


98 


ORGANIC    CHEMISTRY. 


Calcinm  acetate.  Ordinal  y  acetone. 


FORMIC    ACID. 


CH,0,=CH,0 


H 


O. 


Eed  ants  made  to  pass  over  moistened  blue  litmus 
paper  produce  red  stains.  Tiie  acid  secreted  by 
these  insects  was  first  obtained  by  Gehlen,  and  lias  re- 
ceived the  n:;nie  oi  formio  add. 

I.  Berthelot  has  obtained  it  from  carbon  mon- 
oxide by  synthesis. 

II.  It  is  prepared  by  distilling  a  mixture  of  10 
parts  of  starch,  30  parts  of  sulphuric  acid,  20  parts  of 
water,  and  37  parts  of  manganese  biuoxide  in  a  large 
retort  connected  with  a  condenser. 

The  mass  swells  considerably,  and  at  first  must  be 
heated  but  gently.  The  fonnic  acid  is  distilled  over 
and  saturated  with  lead  carbonate.  The  fbrmiate  of 
lead  is  caused  to  crystallize  m  boiling  water,  then 
placed  in  a  retort  and  decomposed  by  a  current  of  hy- 
drogen sulphide  and  thereupon  heated;  the  formic  acid 
is  then  distilled  oif. 

III.  One  kilo  of  glycei-ine,  150  to  200  grains  of  water 
and  1  kilo,  of  oxalic  acid  are  introduced  into  a  retort 
and  heated  for  15  iiours  at  a  temperature  of  about  100°. 
The  oxalic  acid  is  decom]30sed,  but  only  carbon  di- 
oxide is  disengaged.     "Water  is  added  from  time  to 


ACKTIO    ACID. 


9» 


lue  litmus 
creted  by 
iiid  lias  re- 

bon    inon- 

ture  of  10 
10  parts  of 
in  a  large 

3t  must  be 
tilled  over 
>rmiate  of 
ater,  then 
rent  of  liy- 
ormic  acid 

ns  of  water 
:o  a  retort 
bout  100°. 
jarbon  di- 
a  time  to 


time,  and  the  mixture  then  distilled  until  8  litres  have 
passed  over.  The  glycerine  remains  unchanged  in  the 
retort,  and  can  again  be  used. 

Fonnic  acid  is  a  colorless  liquid,  of  a  very  acid  re- 
action, a  pungent  odor  and  crystallizing  at  about  0° 
and  boiling  at  104°. 

It  reduces  oxide  of  mercury,  furnishing  mercury,  as 
a  brown  powder,  also  carbon  dioxide  and  water.  Its 
salts  are  usually  soluble,  though  that  of  lead  is  very 
little  soluble  in  cold  water,  but  quite  soluble  in  boil- 
ing water. 

On  heating  with  sulphuric  acid,  carbon  monoxide 
and  water  are  formed. 

Exi'KEiMEOT, — Introduce  into  a  test-tube  a  small 
quantity  of  formic  acid  or  a  formiate.  Add  sulphuric 
acid  and  heat;  a  regular  liberation  of  a  gas  takes  place, 
which  may  be  ignited,  producing  a  blue  flame. 

CH2  02  =  CO+HA  ♦ 

i 

ACETIC  ACID. 

C,HA=CaIl30(^ 
H  \  ^• 

8p.  Gr.  1.08.    Density  of  vapor  30. 

Glacial  acetic  acid  melts  at  17o;  boils  at  118". 

This  is  the  acid  of  vinegar,  and  of  which  it  forms 
the  essential  part.  It  is  found  in  the  juices  of  many 
plants  and  in  certain  fluids  of  the  body.  It  is  formed 
by  synthesis  from  methyl,  sodium,  or  potassium  for- 


100 


OROANIC    CIIKMI8TRY. 


miate,  and  by  the  oxidation  of  acetylene;  also  by  the 
action  of  nitric  acid  upon  fatty  substances,  and  by  the 
reaction  of  potassa  ujxtn  tartaric,  malic  and  citric  acids. 
It  is  further  produced: 

I.  By  the  oxidation  of  alcohol  in  the  following  way: 
"Wine  in  vat!>,  or  casks,  is  placed  in  a  cellar  main- 
tained at  a  temperature  of  about  30°;  every  sixth  or 
eighth  day  several  litres  of  vinegar  are  withdrawn  and 
replaced  by  an  etjual  quantity  of  wine. 

Pasteur  has  established  that  the  oxydation  of  alco- 
hol is  produced  by  a  minute  plant,  the  MtjGoderma 
aceti.  In  fact,  aeetification  commenceu  only  when 
this  plant  has  been  formed  in  the  liquid.  If 
its  development  is  interrupted  the  oxydation  stops;  it 
rendei's  the  service  of  taking  oxygen  fr<jni  the  air  and 
transferring  it  to  the  alcohol. 

This  process  is  very  slow.  It  may  be  rendered  more 
rapid  by  poui-ing  dilute  alcohol  on  beach-wood  shav- 
ings pl'dced  in  bairels.  The  air  penetrates  through 
openings  made  in  the  lower  portion.  The  alcohol, 
after  liaving  been  passed  over  the  shavings  four  times, 
will  be  found  sufhcicntly  acetified,  if  the  temperature  is 
maintained  at  about  25°. 

II.  DiSTILr.ATION    OF    WOOD.      PtROLIGNEOTTS     AOID. 

Wood  is  distilled  in  retorts  ;  yielding  vapors  and  gases. 
The  former  are  condensed  by  causing  them  to  pass 
through  a  condenser  ;  the  gases  are  conducted  under 
the  retoi'ts,  where  they  are  burned,  and  the  heat  util- 
ized in  the  distillation  of  the  wood. 

The  condensed  liquids  are  water,  acetic  acid,  wood 


ACETIC    ACID. 


101 


Iso  by  the 
nd  by  tlie 
Itric  acids. 

wing  way: 
liar  main- 
y  sixth  or 
Jrawn  and 

a  of  alco- 
'^ycodcrma 
Jiily  when 
quid.  If 
1  stops;  it 
le  air  and 

lered  more 
ood  shav- 
8  through 
e  alcohol, 
aur  times, 
lerature  is 

3tT8     AOID. 

and  gases. 

a  to  pass 

ted  under 

heat  util- 

icid,  wood 


spirit  and  tar ;  the  greater  portion  of  the  tar  is  me- 
chanically removed  and  the  remaining  liquid  distilled 
in  a  water  bath.  The  wood  spirit,  which  boils  at  63" 
passes  into  the  receiver.  The  water  and  acetic  acid 
remaining  in  the  retort  are  saturated  with  sodium 
carbonate,  the  product  is  evaporated  to  dryness  and 
heated  from  250°  to  350° ;  this  temperature,  while  not 
effecting  the  decomposition  of  the  sodium  acetate 
is  suiiicient  to  carbonize  the  tarry  substance  remaining 
in  solution.  Tlie  mass  is  thereupon  dissolved  in  water, 
filtered,  and  the  acetate  allowed  to  crystallize.  If  it  is 
desired  to  obtain  the  acetic  acid  uncombined,  the  solu- 
tion of  tile  salt  is  distilled  with  a  slight  excess  of  sul- 
phuric acid. 

The  acetic  acid  which  distils  over  contains  a  large 
amount  of  water.  Normal,  or  anhydrous  acid  may  be 
obtained  from  it  by  saturating  half  of  the  liquid  with 
sodium  carbonate,  then  adding  the  remainder  to  this 
solution ;  acid  sodinni  acet.ite  is  thereby  produced, 
which  is  evaporated  to  dryness  and  distilled  with  sul- 
phuric acid.  This  liquid ,  cooled  with  ice,  gives  crystals 
of  normal  acetic  acid,  which  can  be  separated  on  de- 
canting the  liquid,  furnishing  the  so-called  glacial 
acetic  acid. 

Acetic  acid  is  liquid  above  17";  below  that  it  crys- 
tallizes in  handsome  plates.  It  is  a  strong  acid,  has  a 
pronounced  odor,*  and  is  very  caustic,  producing  blis- 
ters on  the  skin.  It  is  soluble  in  water,  alcohol  and 
ether  in  all  proportions.  It  dissolves  resin  and  cam- 
phor, also  fibrin  and  coagulated  albumen.     On  imiting 


102 


ORGANIC    CHEMISTRY. 


with  M'ater  it  contracts  in  volume.  A  red  lieat  de- 
stroys it,  many  products  being  formed;  methane, 
acetylene,  acetone,  benzol,  najjlithalin,  etc.,  also  car- 
bon, which  remains  in  the  retort. 

If  a  flask  containing  chlorine  gas  and  a  small  quan- 
tity of  acetic  acid,  is  exposed  to  the  sunlight,  trichlor- 
acetic acid  is  formed.  ^aClaO )  ^^  ^pj^.^  experi- 
ment of  Dumas  served  as  a  basis  for  the  theory  of 
substitution.     Le  Blanc  has  also  detained  monochloi-- 

acetic  acid  CaH.  CIO  i  ^^     m         1 1    . 

jj  j-  U.     Ihese  chlonne  products  are 

reduced  to  the  state  of  acetic  acid  by  reducing  agents, 
such  as  sodium  auialgam  in  presence  of  water, 

(H2)s-fC2HClA=3HCl-fC.,Il40.,. 

In  the  same  manner  as  acetic  acid,  heated  with  an 
excess  of  a  base,  furnishes  marsh  gas,  trichlor, 
acetic  acid  produces  trichlorinated  marsh  gas,  wliich 
is  chloroform, 

CaHjOa+BaO^BaCOa  +  CR^ 
C2HCl802+BaO=BaC03 + CHCls. 

Perchloride  of  phosphorus,  in  the  hands  of  Gerhardt, 
has  become  the  means  of  an  important  discovery,  that 
of  acetic  anhydride  and  in  general  of  the  anhydrides 
of  the  monobasic  acids.  If  dry  sodium  acetate  (3 
parts)  is  mixed  with  the  perchloride.  or  better,  with  oxy- 


VINEGAR. 


103 


red  lieat  de- 
id;  methane, 
etc.,  alsocar- 

i  small  quan- 
ght,  trichlor- 

This  experi- 

;he  theory  of 
I  monochlor- 

pi'oducts  are 

icing  agents, 
rater, 


ited  with  ,in 
as,  trichlor, 
1  gas,  which 


Ola. 

5f  Gerhardt, 
covery,  that 
anhydrides 
t  acetate  (3 
Br,\vitlioxy- 


chloride  of  phosphorus,  (1  part),  and  then  distilled,  a 
chloride  is  obtained  called  acetyl  chloride, 

C.IIaOCl-CII.O  ) 

CI    f 

acetyl  being  the  radicle  of  acetic  acid.  This  chloride, 
subjected  to  the  action  of  an  excess  of  sodium  acetate, 
is  decomposed  and  furnishes  acetic  anhydride, 


C,IL,0  )  .. 
CUlaOf^'' 


(also  called  acetate  of  acetyl)  or  acetic  oxide,  which 
boils  at  139°.  Water  destroys  it,  acetic  acid  being 
proiluced.  Chloride  of  acetyl  is  an  irritating  liquid, 
boiling  at  about  158°,  decomposable  by  water  into 
acetic  and  hydrochloric  acids. 

A  derivative  of  acetic  acid  of  considerable  theoretical 
importance  is  cyanacetic  acid  C3H3N02=C2H30  \  .. 

CNf^' 
a  crystalline  body  forming  salts  with  the  metals,  which 
have  been  studied  by  T.  Menies.  On  acting  with  sul- 
phuric acid  and  zinc  on  cyanacetic  acid,  the  author 
[82-67-69]  obtained  formic  and  acetic  acids  and  am- 
monia. 

ViNKOAB.  This  name  is  given  to  the  mixture  which 
is  obtained  by  the  acetification  of  wine,  whiskej^,  infu- 
sion of  malt,  etc.  Good  acetic  vinegar  is  of  an  agree- 
able taste  and  aroma.  Wood  vinegar  has  a  very 
strong  disagreeable  taste  and  odor.     It  is  frequently 


104 


ORGANIC    CHEMISTRY. 


I?' 


adulterated  with  sulphuric  acid.  An  addition  of  -,  j^^^ 
of  its  weight  of  this  acid  is,  however,  not  considered 
fraudulent,  as  its  presence  is  regarded  necessary  to 
prevent  moulding. 

A  ready  method  of  detecting  mineral  acids,  pro- 
posed by  M.  Witz  (77-75-268),  is  based  upon  the  use 
of  methyl-aniline,  which  undergoes  no  change  in  con- 
tact with  acetic  acid,  but  promptly  changes  to  a  green- 
ish-blue in  presence  of  the  least  trace  of  mineral  acid. 

Vinegar  and  concentrated  acetic  acid  are  employed 
in  medicine  as  stimulants. 

An  acetate,  or  acetic  acid,  can  be  recognized  by  heat- 
ing it  slightly  with  sulphuric  acid  and  alcohol ;  a 
fragrant  odor,  characteristic  of  acetic  ether,  is  observed. 
Heated  with  sulphuric  acid  alone,  the  acetates  liberate  a 
vapor  which  has  tlie  odor  of  vinegar. 

The  following  reaction  permits  of  the  detection  of 
mere  traces  of  acetic  acid;  it  is  saturated  with  potas- 
sium carbonate  and  heated  with  arsenous  oxide  in  a 
test  tube;  fumes  and  a  nauseating  odor  are  given  off. 

The  author  finds  that  one  of  the  simplest  tests  for 
acetic  acid,  is  to  direct  a  fine,  yet  powerful  stream  of 
water  into  a  test-tube,  containing  a  few  drops  of  the 
liquid  to  be  tested.  The  very  fine,  white  efferves- 
cence resulting  is  entirely  characteristic  of  this  acid, 
notie  of  the  other  oi-dinary  acids  producing  the  same 
effect. 

Alcohol  should  not  be  present,  as  it  causes  a  similar 
effervesence.  If  the  acetic  acid  is  combined  it  should 
be  set  free  with  a  strong  mineral  acid.    By  this  test, 


''!,^w»l^.:^'His-' 


ACETATES. 


105 


cjonsidered 
cessary  to 

icids,  pro- 
n  the  use 
ige  in  con- 
0  a  green- 
leral  acid, 
employed 

id  by  lieat- 

loohol ;   a 

observed. 

\  liberate  a 

stection  of 
ith  potas- 
xide  in  a 
ven  off. 
;  tests  for 
stream  of 
>ps  of  the 
efferves- 
this  acid, 
the  same 

i  a  similar 
it  should 
this  test, 


perliaps  more  physical  than  chemical,  acetic  acid,  di- 
luted  with  1000  parts  of  water,  can  be  readily  recog- 
nized, and  with  practice,  one  part  in  1500.  * 

ACETATES. 

Acetic  acid  is  monobasic;  there  are,  however,  alka- 
Ime  biacetat^s  and  some  basic  acetates  of  copper  and 
lead.  '^ 

POTASSIUM    ACCTATE. 

This  salt,  distilled  with  its  weight  of  arsenous  oxide, 
furnishes  a  very  inflammable  liquid,  formerly  called  the 
"liquor  of  Cadet,"  and  in  wiiich  Bun.en  has  found  a 
radicle  spontaneously  inflammable,  cacodi/l,  CjEjaAs^. 

Potassium  acetate  forms,  as  well  as  sodium  acetate, 
an  acid  acetate  when  treated  with  acetic  acid.  It  is  a 
very  deliquescent  salt,  diflicultly  crystallizable. 

AMJIONIUM  ACETATE 

NHAHsOa,  / 

Is  prepared  by  saturating  ammonium  carbon- 
ate with,  acetic  acid.  Its  solution  constitutes  the 
spirit  o/Mindererua ;  treated  with  phosphoric  oxide  it 
forms  cyanide  of  methyl.  There  is  also  an  acid  salt, 
NH4CjH80,CaH40.    in  compounds  of  this  character, 


106 


ORGANIC    CHEMISTRY. 


acetic  acid  must  be  considered  as  acting  the  same  part 
as  the  water  of  crystallization  in  salts. 

SODIUM   ACETATE. 

NaC^HsOa+SlIjC). 

This  is  used  in  preparing  marsh  gas  and  concentrated 
acetic  acid.  It  is  recommended  by  Tommase  (62-72- 
23),  as  a  solvent  for  plumbic  iodide,  of  which  two  grams 
are  readily  dissolved  in  0.5  c.  c.  of  a  strong  sokition  of 
sodium  acetate. 

CALCIUM  ACETATE. 

Ca(C2HAV 

This  salt,  subjected  to  distillation,  ftimislies  a  liquid 
containing  a  large  proportion  of  acetone  CsHgO- 

ALUMINUM  ACETATE. 


A1(C,H30,)3. 

This  body  is  employed  at  present  by  dyers,  as  a  mor- 
dant. It  is  prepared  by  causing  aluminum  sulphate 
to  react  upon  lead  acetate.  Lead  sulphate,  which  is 
insoluble,  is  separated  on  filtering  the  liquid. 

FEKBIC  ACETATE. 

Tliis  salt  {pyroUgnite)  has  been,  and  is  still, 
somewhat  employed  for  the  preservation  of  wood. 


ACETATES 


107 


same  part 


icentrated 
se  (62-72- 
two  grams 
solution  of 


es  a  liquid 
T.O. 


,  as  a  mor- 
i  sulphate 
(,  which  is 


1  is  still, 
wood. 


COPPKR   ACETATES. 

I^omml  acetate  CAx{C,n,0,),  is  called  verditer.  It 
terms  beautiful  green  crystals  (cri/stals  of  Venus), 
which,  subjected  to  distillation,  furnish  acetic 
aeid  mixed  with  acetone.  During  this  operation,  a 
white  sublimate  is  formed,  which  deposits  in  the  neck 
oftheretort.  This  latter  is  cuprous  acetate,  and  is  car- 
ned  over  into  the  receiver,  oxydizes,  and  changes  into 
cupnc  acetate,  which  colors  the  distillate  blue.  There 
remains  in  the  retort,  after  this  decomposition,  very 
finely  divided  copper  which  takes  fire  when  slightly 
heated  in  the  air.  Solutions  of  this  acetate  reduce  the 
salts  of  tne  oxide,  CuO,  and  serve  to  prepare  the  sub- 
oxide, CujO. 

^   A  basic  acetate,  designated  by  the  name  of  verdigris 
18  obtained  by  exposing  to  tlie  air  sheets  of  copper 
moistened  with  vinegar,  or  surrounded  by  the  maro  of 
grapes.     The  metal  becomes  covered  with  a  greenish 
incrustation  whose  formula  is, 

Cu(02H3O2)j,CuO4-6H2O. 

LEAD    ACETATE. 

The  normal  acetate  Pb(C  JI3O,),  is  prepared  by  treat- 
ing litharge  with  acetic  acid  in  slight  excess.  This  salt, 
known  by  the  name  of  sugar  of  had,  crystallizes  in 
oblique  rhombic  prisms,  soluble  in  two  parts  of  water 
andeight  parts  of  95  per  cent,  alcohol.  It  has  a  sweet 
taste,  and  is  very  poisonous.    It  is  employed  as  a  re- 


108 


ORGANIC    CHEMI8TBY. 


agent,  also  to  prepare  aluminum  acetate  and  lead  cliro- 
raate. 

In  digesting  acetic  acid  with  an  excess  of  litharge,  it 
furnishes  a  hexabaeic  acetate  of  lead.  If  ten  parts  of 
normal  acetate,  with  seven  partsof  litharge  are takeuand 
this  mixture  digested  with  30  parts  of  water,  there  are 
formed  minute  needles  of  a  tribasic  salt  P^CallsOj).^} 
Pb02,  HaO.  Finally  this  salt,  dissolved  in  normal  ace- 
tate, gives  a  sesquibasic  acetate,  which  is  deposited  in 
crystals,  2(Pb2C2H302),PbO,Il20. 

Goulaed's  kxtraot  is  a  solution  containing  a  mix- 
ture of  normal  and  of  sesquibasic  acetate  of  lead, 
which  is  prepared  by  boiling  80  i-arts  of  water,  7 parts 
of  litharge  and  6  parts  of  normal  acetate  of  lead. 


BUTYKIO  ACID. 


C^HsO,^ 


AH.O|o. 


It  is  usually  prepared  as  follows:  a  mixture  of 
10  parts  of  sugar,  1  part  of  white  cheese,  10  parts  of  chalk, 
and  some  water,  is  maintained  at  a  temperature  of  30" 
to  35°.  First,  lactate  of  lime  is  formed,  which  causes 
the  mass  to  thicken,  then  that  salt  changes  into  buty- 
rate,  disengaging  hydrogen  and  carbon  dioxide.  When 
the  mixture  has  become  clear,  the  liquor  is  evaporated 
and  the  butyrate  separated  with  a  skimmer.  This 
salt  is  decomposed  by  concentrated  hydrochloric  acid 
which  separates  the  butyric  acid  in  the  form  of  an  oil, 
which  is  distilled  off.  It  boils  at  163°.  It  is  of  a 
fetid  odor,  and  soluble  in  water,  alcohol  and  ether. 


h 


VALEKIC    ACID. 


109 


lead  cliro- 

itharge,  it 
in  parts  of 
itakeuand 
,  there  are 

ormal  ace- 
posited  in 

ing  a  tnix- 
I  of  lead, 
er,  7  parts 
ead. 


[lixture  of 
ts  of  chalk, 
ture  of  30<* 
ich  causes 
into  buty- 
de.  When 
evaporated 
ler.  This 
hloric  acid 
L  of  an  oil, 
It  is  of  a 
id  ether. 


Valerianic,  or  Valeric  Acid  CgHjoOj  =  ^s'^'^  I O. 

It  can  be  obtained  by  oxydizing  amylic  alcohol  by 
a  mixture  of  potassium  bichromate  and  sulphuric  acid 
or  by  distilling  valerian  root  with  water  acidulated 
with  sulphuric  acid.  The  best  method  is  to  boil  por- 
poise oil  with  water  and  lime.  The  oil  saponifies  and  the 
valerianate  of  calcium  alone  is  dissolved.  This  liquid 
is  concentrated  and  hydrochloric  acid  added  in  excess. 
The  valerianic  acid  separates  out  in  the  form  of  an  oil 
wliich  is  distilled,  and  that  portion  collected  which 
passes  over  at  175°. 

Pierre  and  Puchot  have  lately  devised  a  process  for 
preparing  valeric  acid  from  amyl  alcohol.     (3-[3]6-40. ) 

benzoic  ACID,  C7He02. 

Density,  61. 

Density  of  iu  vapor  compared  with  air,  4.27.  •  . 

Melts  at  120°;  boils  at  250°. 

It  is  obtained  by  a  dry,  as  also  by  a  wet  process. 
To  prepare  it  by  the  former  method,  equal  weights  of 
sand  and  gum  benzoin  are  placed  in  an  earthen  ves- 
sel, the  mixture  covered  with  a  sheet  of  filter  paper, 
which  is  pasted  down  round  the  edge,  and  a  long  cone 
of  M'hite  cardboai-d  placed  over  the  whole.  The 
earthen  vessel  is  then  heated  ovqr  a  slow  fire  for  two 
hours,  and  when  cool  the  cone  is  removed.  The  ben- 
zoic acid  is  found  to  have  condensed  on  the  interior 
of  the  cone  in  handsome  blades,  or  needles. 


110 


ORGAXIC    0HEMI8TBT. 


It  is  obtained  in  the  wet  way,  by  piilverizing  gum 
benzoin,  mixing  it  with  half  its  weight  of  lime,  and 
boiling  for  half  an  hour  in  a  cast-iron  kettle,  with  six 
times  its  weight  of  water,  care  being  taken  to  agitate 
the  mixture.  It  is  thrown  upon  a  piece  of  linen  and 
the  residue  treated  twice  with  water.  The  liquids  are 
reduced  in  volume  to  two-thirds  that  of  the  water  used 
during  the  first  treatment,  then  saturated  with  hydro- 
chloric acid.  The  benzoic  acid  sepanitcs  out,  and  is 
recrystallized  from  a  solution  in  boiling  water. 

It  is  also  procured  from  the  urine  of  horbivorous 
animals.  This  secretion,  evaporated  to  a  small  bulk 
and  treated  with  hydrochloric  acid,  yieMs  a  deposit  of 
hippuric  acid,  which,  on  being  heated  with  dilute  sul- 
phuric acid,  is  transformed  into  benzoic  acid. 

Benzoic  acid  is  also  produced  on  a  large  scale  from 
naphthalin. 

Benzoic  acid  crystallizes  in  lustrous  blades,  or  need- 
lesjis  little  soluble  in  cold  watiT,  quite  soluble  in  boiling 
water,  and  still  more  so  in  alcohol  and  ether.  On 
passing  its  vapors  through  a  tube  heatod  to  redness,  it 
is  decomposed  into  benzol  and  carbon  dioxide, 
C7H,02  =  CjHg-}-COj.  Chlorine,  bromine  and  nitric 
acid  transform  it  into  substitution  products. 

Chlorbenzoic  acid,  C7H5CIO. 
Dinitrobenzoic  "    C7li4(NO.,)20j. 

Ammonium  benzoate  furnishes,  on  distillation,  benr 
zonitrile  C^NHsOa  =  C^HjN  +  2HoO. 

The  alkaline  benzoates  heated  with  chloride,  or 


BENZOIC   ACID. 


Ill 


Zing  gum 
lime,  and 
,  with  six 
to  Agitate 
[inen  and 
quids  are 
'ater  used 
th  hydro- 
lit,  and  is 

rbivorous 
nail  bulk 
leposit  of 
lilute  sul- 

cale  from 

,  or  need- 
in  boiling 
lier.  On 
edness,  it 
dioxide, 
nd  nitric 


;ion,  hen- 
aridc,  or 


oxychloride  of  phospliorus,  furnish  benzyl  chloride, 
which,  submitted  to  the  action  of  potassium  benzoate 
in  excess,  gives  benzoic  anhydride, 

3(KC,H50j)+POCl8  =  3(C7H50C1)+K3P04. 

^ , ' 

Chloride  of  benzyl. 

C,H50C1+KC;HA  =  C„H,o03+KCl. 


Benzoic  anhydride. 

The  rational  formula  of   benzoic    anhydride    is, 


CJI5O),. 
C:H,0  [  "• 


Calcium  benzoate  heated  to  a  high  temperature 
furnishes  henzone, 

Ca(C,n502>j=  CaC08+C0(CeH,V 

Calcium  benzoate.  Benzooe. 

Benzoic  acid  is  monobasic,  and  the  benzoates  are 
generally  soluble.  Benzoic  acid  taken  into  the  stom- 
ach, is  transformed  into  hippuric  acid. 

Eolbeand  von  Meyer  have  observed  that  benzoic 
acid  has  antiseptic  power,  though  less  than  salicylic 
acid,  (18-[2J  12-133). 

ciNNAMio  ACID.  In  Certain  balsams  there  exists  an 
acid  called  cinnamio  acid,  wiiose  formula  is  CJIgOa. 
It  exists  in  the  balsams  of  Peru,  benzoin,  tolu  and  in 
liquid  storax.     It  fuses  at  129"  and  boils  at  290°.     It 


112 


ORGANIC     CHEMISTKY. 


has  striking  features  of  resemblance  to  benzoic  acid, 
and  is  produced  like  the  latter  l.y  the  oxydation  of  an 
aldeliyd.  This  aldehyd  is  the  essence  of  cinnamoa 
prepared  by  distilling  cinnamon  with  water. 

POLYATOMIC  ACIDS. 

OXALIC   ACID. 


c,ha=^^hI  I  ^^ 


PEEPARATioy.  In  the  burdock  and  sorrel  is  found 
an  acid  salt,  commonly  called  salt  of  sorrel,  which  is 
a  mixture  of  binoxalate  and  quadroxalate  of  potas- 
sium. Sodium  oxalate  is  found  in  several  marine 
plants,  calcium  oxalate  in  the  roots  of  tlie  gentian 
and  rhubarb,  and  in  certain  lichens.  Salt  of  sonul  is 
extractecl  from  the  burdock  {Prunex\  in  Switzerland, 
and  in  the  Black  Forest  of  Germany,  by  exprtssising 
the  jilfint,  clarifying  the  expressed  liquid  by 
boiling  with  clay,  and  evaporating  ;  crystals  of  salt  of 
sorrel  are  deposited. 

The  oxalic  acid  maj'  be  obtained  free  by  decompos- 
ing a  solution  of  these  crystals  with  lead  acetate ; 
the  oxalate  of  lead  which  precipitates  is  treated  with  a 
suitable  quantity  of  sulphuric  acid ;  the  lead  is  com- 
jjletely  precipitated  as  lead  sulphate  ;  this  is  filtered 
off,  and  the  liquid  evaporated  and  allowed  to  crys- 
tallize. 

At  present  this  acid  is  chiefly  prepared  by  the  action 
of  oxydizing  agents  upon  certain  organic  substances; 
the  substances  best  suited  for  tliis  purpose  are  those 


OXALIC    ACID. 


118 


izoic  acid, 
tion  of  ail 
cinnamon 


I  is  found 
,  which  is 
of  pcitas- 

II  marine 
3  gentian 

sorrcl  is 
itzerland, 
xpressing 
iqiiid  l)y 
of  sal  t  of 

ieconipos- 
acetate ; 
ed  with  a 
id  is  corn- 
is  filtered 
.  to  crys- 

the  action 
hstances ; 
are  those 


which  contain  oxygen  and  lijdrogen  in  the  proportion 
to  form  water.  One  part  of  starch,  or  sugar,  is  l)oiled 
with  eight  parts  of  nitric  acid  diluted  with  ten 
parts  of  water,  until  nitrous  vapors  cease  to  be  disen- 
gaged, and  the  liquid  then  evaporated.  The  crys- 
tals of  oxalic  acid  which  separate  out  are  freed  from 
the  excess  of  nitric  acid,  by  being  several  times  re- 
crystallized  in  water.  It  is  also  obtained  on  a  large 
scale  by  the  action,  at  a  high  temperature,  of  potassa 
or  soda  on  saw  dust. 

Oxalic  acid  has  been  obtained  synthetically,  by 
Drechel,on  passing  carbon  dioxide  over  sodium  heated 
to  320". 

2COj+Nai=Na,C204. 

Properties. — Oxalic  acid  crystallizes  in  prisms, 
which  effloresce  in  the  air,  and  which  are  very  soluble 
in  water  and  alcohol. 

It  fumes  at  98°;  at  170°  to  180°  it  is  partially  sub- 
limed, but  the  greater  portion  is  decomposed  into  cai-- 
bon  monoxide,  carbon  dioxide,  formic  aciil  and  water. 

2(C2H  A)=CO + 2C0i+C  II,0,+II,0. 

Chlorine,  hypochlorous  acid,  fuming  nitric  acid  and 
hydrogen  peroxide,  convert  oxalic  acid  into  carbon 
dioxide. 

Sulphuric  acid  causes  it  to  split  up  into  carbon  mon- 


114 


ORGANIC     CHEMISTRY. 


oxide  and  carbon  dioxide,  and  this  reaction  is  made  use 
of  in  preparing  the  former  gas. 

Oxalic  acid  is  bibasic. 

Normal  jiotassiuiu  oxalate,  K.^=02=C02 . 
Acid  potassium  oxalate,  KII=02=Cj()2. 

Uses. — Oxalic  acid  is  employed  in  removing  ink 
spots  from  cloth,  and  in  cleaning  copper.  It  owes  these 
}»ro|)ertie8  to  the  fact  that  it  forms  with  iron  and  copper 
soluble  salts,  hence  it  is  also  employed  in  calico-works 
for  removing  colors. 

Toxic  action  of  oxalic  acid.  On  account  of  the  use 
of  oxalic  acid  in  tlie  arts,  and  its  physical  resemblance 
to  cflrtaiu  salts,  particularly  to  magnesium  sulphate, 
poisoning  wiih  it  has  often  occurred,  either  through 
design  cr  imprudence. 

It  acts  powerfully  upon  the  system.  Tai-dieu  men- 
tions the  case  of  a  young  man,  sixteen  years  of  age, 
who  was  poisoned  by  two  grams  of  this  substance. 

The  symptoms  observed  are  similar  to  those  pro- 
duced by  other  corrosive  agents;  great  prostration  fol- 
lowed by  unconscionsness  and  a  persistent  numbness 
in  the  lower  extremities.  The  blood  of  the  patient  be- 
comes abnormally  red. 

In  cases  of  poisoning,  the  acid  should  be  removed 
from  the  stomach  with  promptness,  and  milk  of  lime, 
or  magnesium,  or  ferric  hydrate  administered.  Lime 
is  to  be  preferred,  as  it  forms  a  salt  completely  insol- 
uble in  vegetable  acids. 


■J 


SUCCiNlO     SOW. 


115 


made  use 


O2. 

'2. 

ving  ink 
wes  these 
id  copper 
ico-works 

af  the  use 

emblance 

sulphate, 

through 

ien  men- 
8  of  age, 
ance. 
lose  pro- 
ation  fol- 
lumbness 
atientbe- 

removed 

of  lime, 

1.     Lime 

ely  insoL 


SUCCINIC   ACID. 


CJI,04  =  C4lIA) 
H,) 


O,. 


This  acid  is  produced  by  the  oxydation  of  butyric 
acid,  and  by  subjecting  amber,  succlnum,  to  dry  distil- 
lation or  by  the  action  of  iodhydric  acid  on  malic  or 
tartaric  acids. 

Succinic  acid  crystallizes  in  rhomboidal  prisms  which 
melt  at  180°  and  boil  at  about  235°,  at  a  higiier  tem- 
perature tliey  are  decomposed  into  water  and  succinic 
anhydride  C4H4OS.  It  is  soluble  in  5  times  its  weight 
of  cold  water,  soluble  in  ether  and  very  soluble  in  alco- 
hol. 

It  is  used  in  the  artificial  preparation  of  malic  and 
tartaric  acids.  Succinic  acid  has  been  found  in  the 
fluid  of  the  hydrocele  and  oi  certain  hydatids. 

HALIC   ACID. 

C4H3O2 }  f^ 

Tliis  acid,  discovered  by  Scheele  in  sour  apples,  is 
found  in  many  plants;  in  the  berries  of  the  service- 
tree,  in  cherries,  raspberries,  gooseberries,  rhubarb,  to- 
bacco, etc.  Malic  acid  is  levogyrate,  deliquescent 
and  crystallizable;  it  is  soluble  in  alcohol  and  fuses  at 
about  100°. 

At  a  temperature  above  130°,  it  is  decomposed  into 


lii^ 


116 


ORGANIC    CHZiMISTRY. 


various  acids  and  esY>ed{\l\y  paramalio  acid,  €411404, 
which  i.v  identical  witli  the  acid  of  tlie  fumana.  It 
is  bibasic  like  oxaHc  acid,  but  triatoinic  and  is  dis- 
tinguished from  tliis  acid  by  not  producing  a  turbid- 
ity with  calcium  compounds. 

TARTARIC   ACID. 

This  acid,  obtained  from  wine  tartar  by  Scheele,  in 
1770,  occurs  free  and  combined  with  potassium  in 
many  vegetable  products;  in  the  sorrel,  berries  of  the 
service-tree  and  tamarind,  in  the  gherkin,  potato, 
Jerusalem  artichoke,  etc.  The  grape  is  the  chief 
original  source  of  this  acid. 

One  method  of  prepari?!g  tartaric  acid  is  to  purify 
crude  tartar  by  dissolving  and  clarifying  with  clay, 
which  throws  down  the  coloring  matters:  then  filter- 
ing and  adding  calcium  carbonate,  which  precipitates 
half  of  the  tartaric  acid  as  a  calcium  salt. 

2KHC4H4O«+CaCO3=C.C4H4O8+K2C4H4O«+CO.,+Ha0 

Hydro-potassic         Calcium    Calcium  tartrate.    Potassium 
tartrate.  carbonate.  tartrate. 

The  solution  whicli  contains  the  potassium  tartrate, 
is  filtered  and  calcium  chloride  added  :  the  remainder 
of  the  tartaric  acid  .'s  thus  precipitated  as  a  tartrate 
and  added  to  the  preceding. 


cirl^  €411404, 

^umai'ia.     It 

and  is  dis- 

ig  a  turbid- 


y  Scheele,  in 
3otassium  in 
jerries  of  the 
•kill,  potato, 
is  the  chief 

[  is  to  purify 
g  with  clay, 
:  then  filter- 
precipitates 


)e+CO,+H,0 


lum  tartrate, 
le  remainder 
18  a  tartrate 


TARTARIC    ACID. 

K  AH40e + CaCl2=CaC,H.0«  +  2  KCl. 

Potb88ium  tartrate 


117 


V -^ 

Culciura  tai'trate. 


These  precipitates  are  washed  and  decomposed  with 
sulphuric  acid,  the  calcium  sulphate  is  filtered  ofij  and 
the  liquid  evaporated  to  the  point  of  crystallization. 
This  acid  is  also  called  right  tartaric,  or  dextroracemie, 
as  it  turns  the  plane  of  polarization  to  the  right. 

Kistner  has  obtained  from  certain  tartrates  a  tartaric 
acid  which  is  optically  inactive.  This  a  Id,  called  jpaz-a- 
tartario  or  raoemioaoid,  is  somewhat  less  soluble  than 
dextrotartarlc  acid,  while  the  reverse  is  the  case  with 
its  salts.  It  contains,  moreover,  one  molecnle  of  water 
of  crystallization,  but  does  not  crystallize,  as  does  the 
dextrogyrate  acid,  in  hemihedral  crystals. 

Levogyrate  tartaric  acid  is  prepared  by  evaporating 
a  solution  of  raceraate  of  cinchonia;  the  levogyrate 
tartrate  precipitates  while  the  dextrogyrate  reiuftins  in 
solution;  or  a  solution  of  racemic  acid  is  allowed  to 
stand  witli  a  small  quantity  of  calcium  phosphate,  and 
a  few  spores  of  the  PenGilium  glaueum;  fermenta- 
tion sets  in,  which  destroys  the  dextroracemic  acid. 

Dextrotartaric  acid  crystallizes  in  beautiful  oblique 
prisms  with  a  rhombic  base.  Cold  water  dissolves 
twice  its  weight  of  this  acid;  alcohol  dissolves  it  with 
equal  facility.     It  is  insoluble  in  ethei. 

Tartaric  acid  melts  at  about  180°;  and  furnishes  dif- 
ferent pyrogenous  acids,  chiefly: 

TartaHo  anhydride,  or  Tartrelio  acid,  C4H4O8,  and 

PrjTotartario  acid^  CjIIgOi. 


118 


OROANIO    CHEMISTRY. 


Simpson  synthesized  pyrotartaric  acid  and  Lebedeff 
has  recently  (60-75-100)  sliowii  th:it  this  acid  is  iden- 
tical with  that  obtained  by  heating  tartaric  acid. 

Tartaric  acid  does  not  precipitate  calcium  salts.  It 
produces  a  turbidity  with  lime  water,  but  an  excess  of 
acid  dissolves  it;  by  these  reactions  it  may  be  distin- 
guished from  malic  and  oxalic  acids. 

Tartrates.  Tartaric  acid  is  bibasic.  The  two 
tartrates  of  potassium  are  : 

Normal  potassium  tartrate,  KiCJIiOa 
Hydro  "  «         KC34H50e. 

This  latter  salt  is  obtained  by  purifying  the  tartar 
of  wine  casks,  and  is  called  cream  of  tartar.  It  is  used 
in  the  preparation  of  black  flux,  white  flnx,  potassium 
carbonate,  and  tartaric  acid,  also  largely  in  baking 
powders. 

EooHELLE  Salt.  KNaC4ll408+4a(i.  This  salt  is 
a  double  tartrate  of  potassium  and  sodium,  which  was 
formerly  much  used  as  a  purgative.  It  may  be  pre- 
pared by  mixing  in  a  porcelain  disli,  3500  grams  of 
water  and  1000  grams  of  cream  of  tartar,  this  is  brought 
to  boiling  and  Kodium  carbonate  added  as  long  as  ef- 
fervescence is  produced.  This  solution  is  then  filtered 
and  evaporated  until  it  has  a  density  of  1.38. 

The  salt  crystallizes  in  regular  rhomboidal  prisms; 
it  is  soluble  in  <i\  times  its  weight  of  water,  but  in- 
fioluble  in  alcohol. 

Taktab  emktio.    Tartaric  acid  forms,  with  bases,  a 


EMETICS. 


119 


d  Lebedeff 
eid  is  ideu- 
acid. 

1  salts.  It 
t,i  excess  of 
1  be  distin- 

The  two 


the  tartar 

It  is  used 

potassium 

in  baking 

lis  suit  is 
whicli  was 
lay  be  pre- 
•  grams  of 
is  brought 
ong  as  ef- 
len  filtered 

ial  prisms; 
r,  but  in- 

th  bases,  a 


a  class  of  salts  called  emetics,  the  type  upon  which 
they  are  formed  being  that  of  tartar  emetic.  The 
ordinary  tartar  emetic  has  been  generally  assi^ed  the 
formula  (SbO)'K=Oa=C,H,04,  in  which  the  monad 
radicle  stihyl  takes  the  place  of  one  of  the  basic  hydro- 
gen atoms.  It  is  prepared  by  boiling  for  an  hour  in 
100  parts  of  water,  12  parts  of  cream  of  tartar,  and  10 
parts  of  antimony  oxide.  This  mixture  is  then 
filtered,  evaporated  and  allowed  to  crystallize.  This 
salt  crystallizes  in  rhombic  octahedrons  ;  it  has  a  me- 
talUc  taste,  a  slight  acidity,  and  is  soluble  in  14  parts 
of  cold,  and  about  2  parts  of  boiling  water. 

Crystals  of  tartar  emetic  efl^oresce  on  exposure  to  the 
air. 

A  strip  of  tin  precipitates  the  antimony  as  a  brown 
powder.  Tannin,  and  most  astringents,  precipitate 
the  antimony,  hence  tartar  emetic  should  not  be  ad- 
ministered in  connection  with  this  class  of  bodies. 
This  salt  is  the  most  used  ofthe  antimony  compounds. 

Feero-potassium  tartrate.— Cre:im  of  tartar  is  di- 
gested with  ferrous  hydrate  for  two  hours  at  a  tem- 
perature of  60°.  For  every  100  parts  of  cream  of  tar- 
tar, a  quantity  of  hydrate  should  be  used  containing  43 
parts  of  ferrous  oxide. 

The  product  is  filtered,  the  liquid  received  in  shallow 
plates,  and  kept  at  a  temperature  of  about  45°;  the  salt 
thus  crystallizes  in  brilliant  scales  of  a  garnet  red  color. 
It  dissolves  in  water,  but  is  insoluble  in  strong  alcohol. 
Tartaric  acid  is  often  adulterated  with  alum,  potassium 
bisulphate  and  cream  of  tartar ;  these  substances  may 


120 


ORGANIC    CHEMISTRY. 


all  be  detected  by  means  of  alcohol,  in  which  they  are 
not  soluble. 

Tartaric  acid  is  used  in  making  effervescing  drinks, 
and  as  a  discliarge  by  calico  printers. 

Tartaric  acid  produces  the  same  toxical  effects  as 
oxalic  acid,  though  requiring  much  larger  doses.  The 
blood  of  the  poisoned  person  becomes  red  and  very 
fluid. 

CITEIO    ACID. 


f)   IT  n  =^611408  )  pw 


This  acid  is  found  associated  with  oxalic  and  tartaric 
acids  in  matiy  plants.  It  occurs  in  cherries,  currants, 
raspberries,  oranges  and  lemons. 

It  is  ordinarily  extracted  from  the  juice  of  lemons. 
This  juice  is  allowed  to  stand  until  fermentation  com- 
mences, then  filtered  and  treated  with  chalk  and  milk 
of  lime;  an  insoluble  citrate  of  calcium  is  formed,  which 
is  decomposed  by  sulphuric  acid;  the  calcium  sul- 
phate is  filtered  off  and  the  filtrate  evaporated  and  left 
to  crystallize.  Citric  acid  crystallizes  in  regulai* 
rhombic  prisms;  it  is  soluble  in  three  fourths  its 
weight  of  cold  water;  this  solution,  in  time,  becomes 
covered  with  mould. 

Citric  acid  is  soluble  in  alcohol  and  ether.  Heated 
to  about  175°  it  furnishes  aconitio  aoid, 


C«H„  O, 


CJL().,=^«"« 


H: 


:'i°- 


CITRIC    ACID. 


121 


jh  they  are 

ng  drinks, 

1  effects  as 
0868.  The 
1  and  very 


tnd  tartaric 
8,  currants, 

of  lemons, 
nation  coni- 
i  and  milk 
(tied,  which 
ilciiim  sul- 
ed  and  left 
in  regular 
fourths  its 
e,  becomes 

r.    Heated 


losing  H^O  on  increasing  the  tetnj)erature.  Another 
pyrogeuous  acid,  itaeonio  acid  CJW^  is  formed, 
wliich,  if  heated,  is  transformed  into  citrmonio  acid 
isomeric  with  the  last  mentioned. 

Oxydizing  bodies  destroy  citric  acid,  carbon  dioxide, 
acetone,  etc.,  being  produced.  Fused  caustic  potassa 
resolves  it  into  acetic  and  oxalic  acids. 

CeIIA+H,0=C,HA+2C2HA. 


' ^  I ■ \ 

Oxalic  acid.  Acetic  acid. 


Citric  acid  is  tetratomic  and  tribasic.  It  may  be 
distinguished  from  oxalic  arid  tartaric  acids  by  its  ac- 
tion on  lime  water,  wiiich  it  does  not  precipitate  in  the 
cold,  but  if  boiled  with  an  excess  of  lime  water,  a  pre- 
cipitiite  of  basic  calcium  citrate  is  obtained. 

Magnisium  crTBATE.— This  salt  is  prepared  by  treat- 
ing magnesium  carbonate  with  a  strong  solution 
of  citric  acid  and  pi-ecipitating  this  salt  with  alcohol. 
It  is  much  used  in  medicine  as  a  purgative. 

Citrate  of  iron.— Hydrated  ferric  oxide  is  dissolved 
in  a  luke-warm  solution  of  citric  acid,  and  the  liquid 
evaporated  to  dryness. 

This  body  varies  in  its  composition ;  it  occurs  in 
brilliant  amorphous  scales,  of  a  garnet-red  color. 

Amsionia  orTRATB  OF  IRON.— One  liundred  grams 
citric  acid  are  digested  for  some  time  with  a  quantity 
of  ferric  hydrate,  representing  53  grams  of  ii-on,  and 
16  to  20  gmms  of  aqua  ammonia.  The  liquid  is  then 
filtered  and  evaporated  to  the  consistency  of  a  syrup, 


122 


ORGANIC    CHEMISTRY. 


and  transferred  to  very  shallow  vessels  which  are 
placed  in  drying  ovens.  This  substance  solidifies  in 
scales,  if  the  temperature  at  which  it  is  dried  is  not  too 
liigh  and  the  layers  of  liquid  are  extremely  thin. 


LACTIC  ACID. 


CsH«a 


8^6^S  ' 


H,H  f  ^^  • 


This  acid  was  discovered  by  Scheele,  who  extracted 
it  from  sour  milk.  It  exists  in  many  products  after 
fermentation,  as  sauerkraut,  beet  juice,  and  various 
vegetables,  also  nux  vomica.  It  is  found  in  many  ani- 
mal fluids,  in  the  blood  and  in  the  fluids  which  per- 
meates the  muscular  tissues.  It  is  to  this  body  that  the 
acid  reaction  of  sour  milk  is  due.  Lactic  acid  exti-acted 
from  flesh  forms,  with  certain  bases,  salts  which  diifer 
in  solubility,  etc.,  from  those  formed  with  ordinary 
lactic  acid,  hence  this  acid  is  sometimes  csMed  paralao- 
tic  acid,  also  sarko-laotic  aoid,  from  capKo?  flesh. 

Lactic  acid  may  be  prepared  by  dissolving  sugar  of 
milk  in  butter-milk,  adding  chalk  to  the  mixture,  and 
allowing  it  to  stand  for  eight  or  ten  days  at  a  tem- 
perature of  80°  to  36° 

The  sugar  of  milk  is  sometimes  replaced  by  glucose, 
or  cano  sugar  and  fermentation  favored  by  the  addi- 
tion of  cheese. 

A  special  ferment  {lactic  ferment)  is  developed 
which  is  transformed  into  sugar  and  lactic  acid,  but 
the  fermentation  is  arrested  as  soon  as  the  liquid 


LACTJC    ACID. 


123 


vhich  are 
)iidifle8  in 
[  is  not  too 
thin. 


)  extracted 
lucts  after 
id  various 

many  ani- 
vhich  per- 
3y  that  the 
i  exti-acted 
Inch  differ 
I  ordinary 
\paralao- 
flesh. 

»  sugar  of 
xture,  and 

at  a  tem- 

)y  glucose, 
'  the  addi- 

developed 
'.  acid,  but 
the  liquid 


becomes  acid,  and  it  is  in  order  to  prevent  this  acidity 
that  an  excess  of  calcium  carbonate  or  sodium  bicar- 
bonate is  always  maintained. 

Wurtz  has  produced  this  acid  artificially  by  the 
action  of  platinum  black  on  propylglycol. 

0,+Csir80,=C3He03+H,0. 

' > ' 

Propylglycol. 

Lactic  acid  is  a  colorless,  syrupy  liquid  ;  at  about 
130°  it  is  changed  into  the  anhydride  of  lactic  acid, 
CflHioOg,  and  at  about  250°  it  furnishes  a  crystalline 
body  called  lactide  whose  formula  is  C3ri40j. 

Lactic  acid  posseses  the  property  of  dissolving  cal- 
cium phosphate.  The  lactates  are  soluble  in  water. 
Lactate  of  iron,  (CaHsOg^.Fe,  is  employed  in  medicine. 

UEIC  OK  LirHIC  ACID,  CBH4N4O3. 

Discovei-ed  in  1776,  by  Scheele. 

This  acid  exists  in  human  excretions,  and  in  those  of 
the  carnivora.  In  the  excretions  of  herbivora,  the  uric 
acid  is  replaced  by  hippuric  acid.  Uric  acid  is  present 
in  normal  human  urine  only  in  small  quantity.  The 
urine  of  sedentary  persons,  and  of  those  whose  food  is 
very  nitrogenous  and  quite  substantial,  contains  more 
of  this  substance  than  that  of  individuals  who  lead 
an  active  life,  and  whose  diet  is  less  nourishing.  In 
the  latter  case  the  uric  acid  is  oxydized  and  converted 
into  urea,  hence,  the  proportion  of  the  acid  decreases 
as  the  quantity  of  m-eu  increases  :  whereas  calculi  of 


124 


OKGANIO     CHEMISTRY. 


nric  acid  are  frequently  formed  in  persons  whose  diet 
is  very  nourisliing,  and  whose  occnpation  necessitates 
but  little  muscular  exertion.  The  excreta  of  birds 
contains  a  large  proportion  of  uric  acid,  and  that  of 
snakes  is  formed  almost  exclusively  of  this  body. 

This  acid  may  be  prepared  liy  boiling  a  dilute  al- 
kaline solution  with  guano,  excreta  of  the  boa  con- 
strictor, or  uric  calculi  finely  pulverized. 

The  liquid  is  filtered  and  the  filtrate  supersaturated 
with  hydrochloric  acid ;  the  uric  acid  precipitates  in 
flakes,  which  become  crystalline  on  standing. 

The  author  having  had  occasion  in  1858  to  prepare 
large  quantities  of  uric  acid  from  guano,  found  that  in 
order  to  obtain  the  purest  product,  as  free  from  coloi^ 
ing  matter  as  possible,  it  was  preferable  to  use  sod- 
dium  hydrate  as  a  solvent,  and  carbon  dioxide  as  a  pre- 
cipitant, the  latter  in  sufficient  excess  to  transform  the 
hydrate  into  bicarbonate. 

Crystals  of  uric  acid  are  colorless  and  odorless. 
They  are  nearly  insoluble  in  ether  and  alcohol. 
About  1500  parts  of  boiling  water  are  necessary  to 
dissolve  one  part  of  the  acid. 

On  distillation  uric  acid  yields  urea  and  other  cy- 
anic compounds.  Uric  acid  heated  with  water  and 
lead  dioxide  furnishes  urea  and  a  substance  called  al- 
lantom,  which  has  been  found  in  the  urine  of  sucking 
calves.    Its  formula  is  C4HJK4O8. 

The  same  derivative  of  uric  acid  was  obtained  by 
the  author  in  1858,  also  parabanic  acirJ,  on  heating  uric 
acid  with  manganese  dioxide  and  sulphuric  acid. 
(80-[2]4:4:-218.) 


URIC    ACID. 


125 


vhose  diet 

lecessitates 

a  of  birds 

id  that  of 

body. 

I  dilute  al- 

>  boa  coa- 

jrsaturated 
iipitates  iu 

to  prepare 
ind  thatiu 
roin  coloi- 
;o  nse  sod- 
ie  as  a  pre- 
nsfonn  the 

odorless, 
d  alcohol, 
scessary  to 

other  cy- 
water  and 
I  called  al- 
of  Bucking 

Dtained  by 
eating  uric 
tiuric  acid. 


If  1  p;irt  of  uric  add  be  added  to  4  times  its  weight 
of  nitric  acid  of  a  specitic  gravity  of  1.45,  the  Bolution 
being  kept  cool,  small  crystals  of  a  substance  called 
alloxan  separate  out.  whose  formula  is 

C4H4N2O5+3H2O. 

Woehler  and  Liebig  obtained  from  this  body  a  num- 
ber of  very  interesting  derivations,  alloxantin,  al- 
loxanio  acid,  parabanio  acid,  thionurio  acid,  dia- 
lurio  acid,  and  finally  a  magnificent  purple  crystalline 
Iwdy,  murexide.  A  large  number  of  other  deriva- 
tives have  also  been  obtained  by  other  chemists, 
t^specially  Bayer.  The  rich  color,  murexide,  is  made 
use  of  in  detecting  uric  acid.  For  this  purpose,  traces 
of  uric  acid  are  heated  in  a  watch  glass  for  a  few 
minutes,  with  one  or  two  drops  of  nitric  acid  ;  the  ex- 
cess of  acid  is  evaporated,  and  the  dry  residue  exposed 
to  the  vapors  of  ammonia,  when  a  pni-ple,  or  very 
beautiful  rose  color,  will  appear. 

HIPPURIO   ACID 

C^H^NOa. 

The  urine  of  herbivora  contains  a  large  percentage 
of  this  acid,  which  also  exists  in  a  small  quantity  in 
human  ui'ine.  A  frugivorous  diet  augments  the  pro- 
jiortion  of  this  body.  It  is  prepared  by  boiling  the 
fresh  urine  of  the  horse  (hence  the  name,  from  innoi, 
a  horse),  or  better  from  that  of  a  cow,  with  milk  of 


126 


OKGANIO    CHEMISTRY. 


lime,  which  is  than  filtered  and  evapoiated  to  one- 
tentii  its  volume;  this  is  mixed  witli  a  large  excess  of 
hydrochloric  acid  and  left  to  stand  10  or  12  hours. 
The  impure  hippuric  acid  which  precipitates  is  re-dis- 
solved in  soda  and  re-precipitt,ted  with  hydrochloric 
acid.  Animal  charcoal  may  be  added  to  the  saline  so- 
lution if  the  brown  color  still  remains.  Putrid  urine 
yields  only  benzoic  acid.  Dessaignes  has  prepared 
this  acid  artificially  by  causing  zincic  glycocol  to  act 
on  benzoyl  chloride. 

Zn(C2H4N02), -H  2CtI150C1= 
ZnCl,  -J-  2C2H3[NH(C,H50j02. 

Hippuric  acid  crystallizes  in  colorless  crystals, 
which  require  600  parts  of  cold  water  for  their  solution, 
but  are  very  soluble  in  hot  water  and  alcohol. 

It  is  decomposed  at  240°,  benzoic  and  cyanhydric 
acids  being  found  among  the  products  ci'  distillation. 
Under  the  action  of  oxydizing  agents  it  lamishes  ben- 
zoic compounds;  with  nitrons  acid  it  yields  heuzo-gly- 
colic  acid. 


ALKALOIDS. 


127 


sd  to  one- 
;e  excess  of 
12  hours. 
is  is  re-dis- 
.'d  rod  1  lone 
i  saline  so- 
itrid  urine 
!  prepared 
>col  to  act 


crystals, 
ir  solution, 
I. 

yanhydric 
istillation. 
lishes  ben- 
beuzo-gly- 


ALKALOIDS. 

ABTIFICIAl.   BASKS  OB  ALKALOIDS. 
PRIMARY. 

CJI,„+3N. 


Methylamine 

Ethylainine 

Propylamine 

Butylaraine 

AinylainJne 

Caprylamine 


Acetyl  amine 
Allylaraine 


Cnilon  +  lN. 


Cnllin-a  -N . 


Phenylamine,  aniline   - 

Toluidine 

Xylidine 

Cumidine 


CH^N 
CJl^N 
C3H9X 
C4H„N 

Cr.II,3N 


CeH.N 
C,H„N 
CbH„N 
CJI13N. 


Flitalidamine 


CgHsT^. 


128                      ORGANIC    CHEMIST KY. 

CJI,„_„N. 

h  '  ,■ 

Naphthalaniine     - 

SECONDARY. 

-      CioHc^f^. 

f,'  ' 

Dimethylamine     - 
Methylethylainine     - 
Diethylamiue 

TEKNAKY. 

C3ll«  N 
■     C,H„N. 

Trim  ethy  lam  ine 
Dimethyletbylamine      - 
Methylethylamjlamiiie 

-     C4H„N 

PirOSPHINES. 

• 

Methylpho8pl)ine 
Di  methyl  phosphine 
Trimethylphosphine   - 

CH5P 

-    C,H,P 

C3H9P. 

:-. 

ARSINE8. 

Triethylarsine 

CfiFIisAs. 

i^  ■ 

STIBINES. 

Triethylstibine 

CeH^Sb. 

NATURAL    ALKALOIDS.  129 

PRINCTPAL  NATURAL  ALKALOIDS. 


OF    IIIK   CINCHONAS. 


Qninia,Quinicia  and  QiiinidiaCj,H.,,N,0, 
Ciiiclionia  and  Cinclionid'a     0,oIL,x',o' 

^""»a      ■     -     -      c.«hXo4. 


OF   Ol'ItTM. 


Morphia 

Codeia 

Thebaia 

Narcotina 

Papaverine 

Narceia 


CnH„N()3 

C,9H,iN03 
C^H^K  O. 
C30H21NO, 


OF  THE  STBYCIINOS. 


Strychnia 
Brucia 


C2iH.^NA 
^231128^204. 


OF  THE  80LANACE.B. 


Nicotina 
Atropia    - 
Hvosciaminc 
Solauia 


C10H14N2 
CnHj^NO, 

CnH23N03 

C^sHnN  0x6. 


OF  THE   HEMLOCK. 


Conylia 


CsH„N. 


130 


ORGANIC    CHEMISTRY. 


OF  PEPPKB. 


Piperidine 


AIISCELLANEOUS. 


Aconitina 
Veratria 
Theobromine 
Caffeia 


CjHnN. 


0.«H4oNO 

CHgNA 

CsHioNA. 


The  first  organic  base  isolated  was  iiioi-phia,  obtained 
in  1816,  by  Sertuerner.  In  1819,  Pelletier  and  Ca- 
ventou  extracted  quinia  from  cincliona  bark,  and  showed 
that  the  very  active  plants  used  in  pharmacy  owed  their 
energy  to  com  pounds  capable  of  uniting  with  the  acids, 
and  of  forming  with  them  definite  crystallizable  salts. 

From  that  epoch,  the  number  of  organic  alkaloids  has 
become  very  considerably  augmented;  and  methods 
have  been  discovered  by  which  many  of  the  alkaloids 
are  prepared  artificially.  It  was  Fritsche  who,  in 
1840,  obtained  the  first  artificial  alkaloid  on  distilling 
indigo  with  potassa  ;  he  named  it  aniline.  G«rhardt 
by  similar  methods  prepared  quinole'me,  Cahours 
piperidine^  and,  Chantard  toluidine. 

The  distillation  of  organic  matter  also  furnishes  al- 
kaloids. Thus  several  of  them  have  been  obtained 
from  a  product  of  the  distillation  of  bones,  the  oil  of 
Dippel ;  also  as  products  of  the  distillation  of  vaiious 
other  organic  compounds. 


COMPOUND    AMMONIAS. 


131 


!5H„N. 


UNO 

I52NA 

tsNA 

I10N4O,. 

phia,  obtained 
etier  and  Ca- 
•k,  and  showed 
acy  owed  their 
vith  the  acids, 
allizable  salts. 
3  alkaloids  has 
and  methods 
the  alkaloids 
ache  who,  in 
don  distilling 
le.  G«rhardt 
)'me,  Cahours 

\  furnishes  al- 
been  obtained 
es,  the  oil  of 
don  of  vaiious 


A  very  general  method  is  due  to  Zinin,  which  con- 
sists in  causing  a  reducing  substance  to  act  upon 
nitrous  compounds  as  nitrobenzol,  for  example.  The 
nitrous  compound  is  introduced  into  an  alcoholic  solu- 
tion of  ammonium  sulphide,  and  the  mixture  allowed 
to  stand;  sulphur  is  soon  deposited,  and  the  hydrogen 
of  the  hydi'ogen  sulphide  combines  with  the  oxygen 
of  the  nitrous  compound.     Example: 

CeH^NO.,  +  3H,S=2II,0  -F  3S  +  CJI.N. 

> , ' 

Nitrobenzol. 

For  this  mode  of  reduction,  as  it  is  not  very  prac- 
tical, and  is  tedious  in  execution,  there  is  at  present 
substituted  the  action  of  iron  upon  acetic  acid,  or 
that  of  zinc  or  tin,  on  hydrochloric  acid. 

Wurtz  has  given  a  very  interesting  method,  which 
has  led  to  the  discovery  of  alkaloids  much  resembling 
ammonia,  for  that  reason  called  compound  ammonias. 
It  consists  in  causing  potassa  to  react  upon  the  cyanic 
ethers,  these  bodies  being  decomposed  much  like  cy- 
anic acid. 

Thus  methylamine  is  obtained  by  the  action  of 
potassa  upon  cyanate  oi  methyl  : 


CO 

CH3 


N  +  2KIIO=K,C03+    H  [n. 


" V 

Cyanato 
of  mothyl. 


Potassium 
carlranate. 


Methyl- 
amino. 


Hofmann  made  known,  very  shortly  after  the  pub- 


132 


ORGANIC    CHEMISTRY. 


lication  of  Wiirtz'  process,  a  method  for  the  prepara- 
tion of  the  cotnponiui  ammonias,  by  which  not  only  a 
simple  equivalent  of  hydrogen  is  replaced  by  the 
radicles  (Oils),  (Calls),  etc.,  but  all  the  hydrogen  of 
the  ammonia.  Hofmann's  method  consists  in  causing 
ammonia  to  react  upon  hydrochloric  as  well  as  brom- 
hydric  or  iodhydric  ethers,  particularly  the  latter. 

Let  us  take,  as  an  example,  iodide  of  ethyl  in  con- 
nection with  the  study  of 


KTHYLAAONE. 


Ten  to  15  grams  of  iodide  of  ethyl  and  50  grams  of 
aqua  ammonia  are  heated  in  sealed  tubes  of  green  glass 
placed  in  a  water  bath.    The  following  reaction  occurs: 

CJT,I  +  XI13=C,HhNI. 

When  the  liquid  has  become  homogeneous  it  is 
allowed  to  cool,  then  decomposed  by  a  solution  of  po- 
tassium hydrate,  the  vapors  being  collected  in  water, 
containing  hydrochloric  acid.  The  hydrochloric  acid 
solution  is  evaporated  to  dryness,  and  the  residue  treated 
with  pure  alcohol,  which  dissolves  the  chWrhydride  of 
ethylamine  and  leaves  in  an  insoluble  stato  the  ammo- 
nium cldoride  derived  from  the  excess  of  ammonia 
used.  The  solution  of  chlorhydride  of  ethylamine  is 
evaporated  to  dryness,  and  the  deliquescent  crystals 
obtained  decomposed  by  potassium  hydrate,  M-ith  tho 
aid  of  a  gentle  heat.  The  volatilized  product  is  con- 
densed in  a  cooled  I'eceiver.     In  this  reaction  there  is 


CLASSIFICATION  OF  THE  ALKALOIDS.       133 


he  prepara- 
i  not  only  a 
ced  by  the 
lydrogeii  of 
9  in  causing 
11  as  brom- 
latter. 
liyl  in  con- 


0  grams  of 
green  glass 
tion  occurs: 


leous  it  is 
ition  of  po- 
1  in  water, 
chloric  acid 
idue  treated 
rhydride  of 
I  the  arnmo- 
>f  ammonia 
hylainine  is 
ent  crystals 
e,  M-ith  tho 
hict  is  con- 
on  there  is 


also  formed  diethylamine,  trietliylamine  and  oxide  uf 
tetrethyhinimoniuui  from  which  the  ethylamine  is 
separated  by  distillation. 

It  may  be  obtained  more  readily  by  first  distilling 
1  part  potassium  cyanate  with  2  parts  potassium 
fulphovinate,  then  by  decomposing  the  cyanic  ether 
obtained  with  a  boiling  solution  of  potassium  hydrate 
contained  in  a  flask  connected  with  a  cool  receiver. 

Ethylamine  is  a  limpid  liquid,  with  a  strong  odor 
resembling  that  of  ammonia.  It  has  not  been  solidi- 
fied. It  boils  at  18.7",  and  dissolves  in  water,  producing 
a  very  caustic  solution.  Ethylamine  is  equally  soluble 
in  alcohol  and  ether.  It  is  combustible,  burning  with 
a  blue  flame,  yellow  at  the  margin. 

It  displaces  ammonia  from  its  combinations.  Its 
solutions  give  reactions  similar  to  those  of  ammonia; 
for  instance,  with  salts  of  copper  it  gives  a  bluish  wliite 
precipitate,  which  is  dissolved  in  an  excess  producing 
a  deep-blue  solution. 

It  dift'ers  from  ammonia  in  the  following  reaction: 
ethylamine  precipitates  alumina  from  its  salts,  and 
the  precipitate  is  soluble  in  an  excess  of  ethylamine, 
which  is  not  the  case  with  ammonia. 

CLASSIFICATION  OF    TUE     ALKALOIDS,  OB  ORGANIC     BASES. 

Amines. — Ilofmann  has  given  the  names  of  primary 
amines,  or  monamines,  to  ethylamine,  which  we  have 
just  studied,  and  the  compound  ammonias  in  which  a 
single  atom  of  hydrogen  has  been  replaced  by  a 
radicle. 


134 


ORGANIC    CHEMISTRY. 


r-f:x 


The  same  chemist,  having  prepared  ethylamine  by 
the  action  of  ethj-l  iodide  npon  ammonia,  subse- 
quently succeeded  iii  obtaining  diethylamine  by  similar 
means. 

Tlie  reaction  is  the  following  : 


N 


CoH. 


CoH. 


11  |h 


This  hydroiodide  obtained,  treated  with  potassium 
hydrate  or  lime,  furnishes  a  second  base,  which  is 
biethylammonia,  or  diethylamine ; 


Diethylamine  C4lI„N=N 


A  similar  compound  is. 


Ethylaniline  C8lI„N'=N" 


C2H5. 
H 


These  bases  have  been  given  the  name  of  secondary 
amines  or  imides. 

The  secondary  ammonias  are  attacked  by  ethyl  iodide 
and  other  ethers,  and  u  reaction  takes  place,  iden- 
tical with  that  which  gives  rise  to  the  primary  and 
secondary  aminer,  and  tertiary  amines,  also  called 
nitrlle  bases,  are  thus  obtained. 


AMINES. 


135 


laniine  by 
nia,  subse- 
'  by  similar 


potassiam 
,  which  is 


secondary 

hyl  iodide 
ace,  iden- 
rnary  and 
Iso  called 


Snch  bodies  are: 

rc,ii, 

Tnethylamine  CeIT.5N=N  \  ( '..H,. 

fCITs 
Methylethylphenylaraine  C9H,3N=X^  (\,II, 

These  bases  are  related  to  the  alcohols  in  the  same 
manner  as  the  primary  amines.  Thus  diethylamine  is 
derived  from  the  action  of  2  molecules  of  alcohol  on  1 
molecule  of  ammonia  and  the  elimination  of  2  mole- 
cules of  water: 

2(C,H«0)  +  NIl3-2H20=C4H„N. 

In  like  maimer  the  ternary  amines  may  be  consid- 
ei-ed  as  derived  from  3  molecules  of  alcohol  and  1  mole- 
cule of  ammonia  with  the  elimination  of  3  molecules 
of  water. 

There  are  also  bodies  built  upon  the  type  of  two 
and  three  condensed  molecules  of  ammonia,  and  are 
denommated,  respectively,  di  amines  and  tri-amines;  as 

!(C  H  y 


Ternary  ethylene  diamine  IS^ 


(c,H4); 


130 


ORGANIC    CHEMISTKY. 


Triethylainine  attacks  hydroiodic  ether,  and  there  i& 
formed  the  compound  C8HaeXI=N(C2H5)4T.  This 
body  treated  witli  oxide  of  silver,  furnishes  an  oxy- 
genated quaternary  base, 

CgHaoNI + Ag  HO=Ag  I  +  CsH^iNO. 

This  substance  is  very  caustic,  soluble  in  water  and 
acts  as  an  inorganic  alkaline  base  like  potassium 
hydrate,  with  which  body  it  is  also  analagous  in  com- 
position. 


O 


(CaH,),N 


l\o. 


Amides,  Alkalamides.— The  amides  are  bodies  built 
upon  the  type  of  ammonia,  in  which  one  or  more  of  the 
hydrogen  atoms  are  replaced  by  an  acid  compound 
radicle;  thus, 


acetamide  N 


There  are  also  mixed  combinations  of  amides  ard 
amines,  called  alkalamides,  as 


acetanilide  II^" 


Cell, 
CjIIaO. 

H 


and  there  i& 
15)4!.  This 
hes  an  oxy- 


in  water  and 
}  potassium 
;ou8  in  com- 


bodies  built 

more  of  the 

compound 


amides  ard 


ALKALOIDS. 


137 


NATURAL  ALKALOIDS. 

Manj  of  the  natural  alkaloids  appear  to  possess  a 
composition  analogous  to  that  of  the  compound  am- 
monias. Some  are  not  attacked  by  iodide  of  ethvl, 
and  should  be  classified  among  the  ammoniums,  bodied 
having  the  same  relation  to  the  compound  ammonias 
as  does  ordmary  ammonium  hydrate  to  ammonia. 
Others  are  acted  upon  by  iodide  of  ethyl,  and,  from  the 
number  of  bases  furnished,  it  may  be  ascertained 
whether  they  belong  to  the  primary,  secondary  or  ter- 
nary  compound  ammonias. 

The  properties  of  the  natural  alkaloids  in  general, 
resemble  those  of  the  artilicial  bases  or  alkaloids, 
lliey  contain  nitrogen;  those  that  do  not  contain  oxy- 
gen are  ordinarily  volatile,  while  those  with  oxygen  are 
non-volatile;  they  are  very  soluble  in  alcohol,  ether 
and  chloroform. 

Certain  ones  are  dissolved  by  the  hydr^carbides, 
which  are  now  considerably  used  in  the  prepa..*ionof 
the  alkaloids.  Water  does  not  dissolve  any  of  the 
artihcial  alkaloids,  except  those  having  a  very  low 
molecular  weight,  like  ethylamine;  this  liquid,  how- 
ever, dissolves  codeia  and  narceia  quite  readily.  With 
the  exception  of  quinia  and  cinchonia,  they  turn  fhe 
plane  of  a  polarized  ray  of  light  to  the  left. 

They  react  like  atnrnonia,  or  potassa,  with  vegetable 


138 


ORGANIC    CHEMISTRY. 


II 


colors,  and  famish,  with  platinum  bichloride,  crystal- 
lizable  double  chlorides,  little  soluble  and  yellow  in 
color.  They  combine  equally  well  with  auric  and  mer- 
curic chlorides. 

The  natural  alkaloids  have  ordinarily  a  bitter  taste. 
Among  their  salts  the  sulphates,  nitrates,  chlorides 
and  acetates  are  mostly  soluble,  while  the  oxalates, 
tartrates  and  tannates  are  insoluble. 

Tlie  harmless  character  of  tannic  acid,  and  the  in- 
solubility of  the  compounds  formed  by  it,  witli  the  al- 
kaloids, render  tannin  and  astringent  vegetable  sub- 
stances generally  very  efficacious  antidotes. 

The  precipitates  they  produce  are  soluble  in  acid  and 
alkaline  liquids. 

The  alkaloids  are  partially  precipitated  from  their 
solutions  by  potassa,  soda  and  ammonia.  Iodine  water 
and  solutions  of  iodine  in  potassium  iodide,  precipitate 
them  completely. 

According  to  Schultze,  the  liquid  obtained  by  add- 
ing antimony  perchloride  to  a  solution  of  phosphoric 
acid,  is  a  re-agent  which  precipitates  most  of  the  or- 
ganic bases. 

A  delicate  re-agent  for  the  alkaloids  is  the  double 
iodide  potassium  and  mercury.  According  to  Meyer, 
the  best  proportions  are  49  grams  of  potassium  iodide 
and  136  grams  of  mercury  dichloride,  to  1  litre  of 
water.  It  is  best  to  add  the  re-agent  to  the  solution 
of  the  alkaloid,  which  may  be  neutral,  acid,  or  even 
feebly  alkaline. 

It  must  be  borne  in  mind  that  the  presence  of 


le,  crystal- 
yellow  in 
ic  and  mer- 

itter  taste. 
,  chlorides 
B  oxalates, 

ind  the  in- 
nth  the  al- 
3table  snb- 

iu  acid  and 

from  their 
Kline  water 
precipitate 

id  by  add- 
phosphoric 
of  the  or- 

the  doable 
'  to  Meyer, 
iuin  iodide 
1  litre  of 
le  solution 
d,  or  even 

resence  of 


NIOOTIiVA. 


139 


sugar,  tartaric  acid  and  of  albumen  may  mask  the  reac- 
tions  ot  a  number  of  alkaloids. 

NICOriNA  OB  NIOOTYIJA. 

^,f  \'r '°!u'  ""^^^'"^^  ^'■^'"  ^^^'^  i^^icofina  taba- 
^m  for  this  purpose  a  decoction  of  tobacco  is  made, 
and  the  hquor  evaporated  to  a  syrup.  The  extract  is 
t^ated  with  twice  its  volume  of  86  per  cent,  alcohol, 
which  precipitates  the  salts  present  and  certain  organ! 
ic  substances.  ^ 

8„hm?.f  S''.^''"'  "^^""'T  ''  ^'''^^'^  ^"d  *h«  residue 
submitted  to  a  second  similar  treatment.     The  alco- 

tiated  solution  of  potassium  hydrate,  and  the  nicotina 
.barated  is  re-dissolved  in  ether.     This  ethereal  solu- 

S-nT^'^'^'^'.^J"  *  ^**^''  ^**^'«"d  the  residue 
distilled  m  an  oil  bath,  in  an  atmosphere  of  hydrogen 

Nicotina  IS  a  colorless  liquid  when  pure,  remaining 

liquid  at  -lOo,  boiling  at  about  246»,  with  decomposf 

tion.     It  has  the  odor  of  an  old  pipe.     Exposed  to 

the  air  It  becomes  brown,  then  resinous;  water,  alcohol 

Kicotina  is  a  powerful  base;  it  fumes  when  a  rod 
moistened  with  hydrochloric  acid  is  brought  near  if 
It  precipitates  the  metallic  oxides,  l^icotina  requires 
two  molecnles  of  a  monobasic  acid  for  satumtion. 
The  chloride,  C.oII„N,i{IIci,  is  erystallizable,  though 


140 


ORGANIC    CHEMISTRY. 


deliquescent.  The  hydrogen  it  contains  is  not  replace- 
ible  by  methyl,  ethyl,  etc.  It  may  be  considered  as 
having  the  rational  formula, 

^M(05H.)'"; 

(C5H7)' ' '  being  the  compound  radicle  niootyl. 
Proportion  of  nicotina  in  different  tobaccos  : 


Havana, 
Maryland, 
Virginia, 
Lothringen, 


2.0  per  ct. 
2.3      « 
6.9      « 
8.0      « 
(Schloesing.) 


TOI8ONINO   BY  TOBACCO  OB   BY  NICOTINA. 

The  injection  of  a  concentrated  decoction  of  tobacco, 
causes  serious  results  in  a  few  minutes  :  intense  head- 
ache is  pi-oduced,  with  nausea  and  vomiting,  violent 
pain  in  the  abdomen,  pallor,  and,  finally,  extreme 
prostration. 

An  infusion  of  tea,  unroasted  coflfee,  or  any  astring- 
ent substance  (pulverized  nut-galls,  or  oak-bark)  are 
the  only  antidotes  known,  and  they  are  far  from  being 
wholly  reliable. 

The  pure  nicotina  is  one  of  the  most  dangerous 
poisons.  It  manifests  itself  immediately  on  being 
taken,  since  it  is  entirely  soluble  in  water. 

The  nervous  system  is  especially  affected.  Two  or 
three  drops  sulfice  to  cause  death. 


ot  replace- 
isidered  as 


tyl. 

508  : 

!r  ct. 


u 


loesing.) 

NA. 

of  tobacco, 
tense  liead- 
ng,  violent 
y,  extreme 


CONIA. 


141 


f 

my  astring- 
k-bark)  are 
from  being 

- 

danfijerous 
r  on  being 

1     Two  or 

Two  drops  introduced  into  the  throat  of  a  dog  A\-ill 
ahnost  instantaneously  canse  the  following  series  of 
symptoms:  respiration  becomes  difiicnlt,  the  animal 
staggers,  falls  without  the  power  of  rising  again, 
throws  the  head  back  and,  in  a  few  moments,  is  perfect- 
ly paralyzed,  and  death  ensues. 

PIPEEIDINE. 

There  has  been  obtained  from  the  pepper  ( Piper 
longum,  Piper  nigrum  or  Piper  caudatum\  a  body 
crystallizing  in  colorless  prisms  c&Wed pipenne,  whose 
fovmula  is  CnHisNOs.  It  is  a  neutral  substance. 
Wlien  distilled  with  three  times  its  weight  of  soda- 
lime  it  furnishes  piperidine,  a  limpid  liquid  having 
the  taste  of  pepper,  and  also  its  odor,  soluble  in  water 
and  alcohol,  boiling  at  106°. 

Tliis  body  is  alkaline  and  saturates  acids.  It  con- 
tains a  single  atom  of  hydrogen  replaceable  by  methyl, 
ethyl,  etc. 

OONIA,  CONYLIA.  OB  CONINE. 

This  body  is  obtained  from  hemlock  {Conium  mac- 
vlatvm);  the  crashed  seeds  are  distilled  in  a  large  glass 
retort,  with  a  solution  of  potasga,  or  soda^  whereupon  an 
alkaline  distillate  is  obtained.  The  distilled  product  is 
treated  with  a  mixture  of  two  parts  of  alcohol  and  one 


142 


ORGANIC    CHEMISTRY. 


part  of  ether,  which  dissolves  the  sulphate  of  conia  and 
leaves  the  insoluble  sulphate  of  ammonium.  The  ethe- 
real alcohol  is  separated  by  distillation,  potassa  is  added 
to  the  residue,  and  the  mixture  distilled.  Water  and 
conia  pass  over;  the  latter  is  dehydrated  with  po- 
tassa, and  rectified  in  vacuo,  or  in  a  curretit  of  hydro- 
gen gas. 

Conia  is  a  colorless,  oily  liquid;  emitting  an  odor 
of  hemlock.  Water  dissolves  it  but  little,  and  this 
better  when  cold  than  warm.  It  is  very  soluble  in  al- 
cohol and  ether.  It  boils  at  about  210°,  yet  emits  var 
pors  even  when  cold,  for  if  a  glass  rod,  moistened  with- 
hydrochloric  acid,  is  brought  near  it,  white  fumes  are 
produced.  It  is  a  monacidic  base,  voiy  alkaline,  and 
forms  crystallizable  salts.  One  of  its  atoms  of  hydro- 
gen is  replaceable  by  ethyl  or  methyl. 

This  base  is  very  poisonous.  According  to  Christi- 
ason,  ten  ceTitigrams  would  suffice  to  cause  death.  It  is 
classified  among  the  narcotics;  its  action  is  charac- 
terized particularly  by  its  effect  on  the  organs  of  respi- 
ration and  the  left  ventricle  of  the  heart. 

ALKALOIDS  OF  THE  PAPAVEBAOE^. 

The  seeds  of  the  poppy  {Papaver  somniferum) 
yield,  on  incision,  a  milky  sap,  which  dries  up  in  a  day 
or  two ;  this  sap,  when  solidified,  constitutes  opivm. 
There  are  three  leading  varieties  of  opium : 

I.  Opium  of  Smyrna  is  found  in  small  cakes  of 
100  to  160  grams,  frequently  distorted  and  agglutinated 
together  by  reason  of  their  soft  nature,  and  contain  7 


OPIUM. 


143 


'coniaand 
The  ethe- 
la  is  added 
^ater  and 
with  po- 
of hydro- 

»  an  odor 
and  this 
ible  in  al- 
emits  va- 
enedwith* 
runies  are 
%line,  and 
of  hydro- 

0  Christi- 
ith.  It  is 
8  charac- 
8  of  respi- 


to  10  per  cent,  of  water.  The  snrface  is  brown,  but  the 
interior  has  a  fawn  color.  Sometimes  it  is  found  to 
contain  14  to  15  per  cent,  of  morphia,  but  in  other  in- 
stances only  6  to  6.  Good  Smyrna  opium  should  con- 
tain not  less  than  10  per  cent. 

II.  The  opium  of  Constantinople  is  drier  than  the 
preceding.  It  appears  in  commerce  in  flattened,  irreg- 
ular cakes,  almost  always  surrounded  with  poppy- 
leaves.    It  contains  5  to  10  per  cent,  of  morphia. 

III.  The  opium  of  Egypt  is  still  dryer ;  it  is  rarely 
enveloped  in  leaves.  Its  odor  is  feeble,  and  it  contains 
ho  more  than  a  to  7  per  cent,  of  morphia. 

Eecently,  attempts  have  been  made  to  cultivate  the 
poppy  in  Europe,  especially  in  France. 

Opium  contains  the  alkaloids  morphia,  codeia,  the- 
beia,  papaverine,  opianine,  narcotine  and  narceia,  an 
acid  combined  with  these  alkaloids  called  meeonio  acid 
{from  firjMcov,  a  poppy),  a  crystallized  neuti'al  substance 
called  meconine,  wliich,  according  to  Berthelot,  is  a 
complex  alcohol,  and  finally,  various  gummy  and  resin- 
ous compounds. 


niferum) 
)  in  a  day 
8  opium. 

cakes  of 
lutinated 
contain  7 


MOBPHIA   OR   MORPHINE. 

Ci:II,9N()3,  H,0. 

Preparation.  Ten  kilos,  of  opium  are  treated  re- 
peatedly with  water,  and  the  liquors  evaporated  to  the 
consistency  of  a  syru  o. 

The  mass  is  redisso'ved  in  water,  filtered,  and  again 
evaporated.     To  the  Likewarm  liquid  are  added  1200 


144 


OKGANIC    CHEMISTRY. 


I 
iii 


grams  of  anhydrous  calcium  chloride,  dissolved  in 
twice  its  weight  of  water.  A  complex  precipitate  is 
formed,  containing  resins,  coloring  matters,  and  sul- 
phate and  meconate  of  calcium,  which  is  thrown  upon 
a  filter. 

The  filtered  liquid  is  evaporated  over  a  water-bath. 
During  the  concentration,  a  fresh  quantity  of  meconate 
of  calcium  is  separated  by  filtering,  and  the  liquid 
evaporated  to  the  con?istency  of  syrup.  The  liquid  is 
then  acidulated  with  a  small  quantity  of  hydrochloric 
acid,  and  set  aside  in  a  cool  place. 

At  the  end  of  a  few  days,  it  contains  brown  crystals 
of  the  double  chlorhydrate  of  morphia  and  codeia,  con- 
taminated with  a  blackish  liquid;  these  crystals  are 
drained,  pressed,  and  again  dissolved  in  as  little  boil- 
ing water  as  possible.  The  chlorhydrate,  on  cooling, 
deposits  crystals,  which  are  again  dissolved  in  hot 
water  and  decolored  with  animal  charcoal.  After 
heating  to  SO"  or  85",  the  solution  is  filtered,  and  the 
liquid,  on  being  concentrated,  deposits  the  double  chlor- 
hydrate in  pure  white  crystals. 

This  salt  is  again  dissolved  in  boiling  water,  and  the 
hot  liquid  treated  with  ammonia  ;  the  codeia  remains 
in  solution,  while  the  morphia  is  precipitated.  This 
deposit  is  thrown  upon  a  filter  washed  with  cold  water, 
dried,  and  dissolved  in  boiling  alcohol ;  the  morphia 
separates  out  in  crystals  on  cooling. 

It  frequently  contains  some  narcotina,  from  which 
it  is  freed  by  washing  once  or  twice  with  ether,  or 
chloroform,  which  dissolves  the  narcotina,  and  does 
not  affect  the  morphia. 


MORPHIA. 


145 


dissolved  in 
precipitate  is 
ers,  and  buI- 
thrown  upon 

i  water  bath. 
/  of  ineconate 
d  the  liquid 
The  liquid  is 
hydrochloric 

■own  crystals 
I  codeia,  con- 
crystals  are 
as  little  boil- 
(,  on  cooling, 
olved  in  hot 
•coal.  After 
ired,  and  the 
double  chlor- 

ater,  and  the 
ieia  remains 
tated.  This 
1  cold  water, 
the  morphia 

from  which 
th  ether,  or 
a,  and  does 


Pure  morphia,  (from  Morpheus,  in  allusion  to  its  nar- 
cotic qualities,)  crystallizes  in  regular  prisms  witii  a 
rhombic  base,  is  colorless,  soluble  in  500  parts  of  boil- 
ing water,  scarcely  soluble  in  cold.  Forty  to  forty-five 
parts  of  cold  90  per  cent,  alcohol  are  required  to  dis- 
solve one  part  of  morphia;  it  is  insoluble  in  ether. 
Solutioiis  of  morphia  are  very  bittei'. 

Morphia  is  little  soluble  in  ammonia,  while  it  is  dis- 
solved very  readily  by  alkaline  solutions,  and  even  by 
lime  water. 

Under  the  action  of  heat,  it  fuses  in  its  water  of 
crystallization,  the  latter  escaping,  and  the  alkaloid  re- 
crystallizes  on  cooling. 

Morphine  is  an  energeti'*  reducing  agent,  reducing 
gold  and  silver  salts,  setting  free  the  respective  metals. 
It  separates  the  iodine  from  solutions  of  iodic  acid. 
If  a  solution  of  starch  is  poured  into  a  test-tube,  and  a 
solution  of  iodic  acid  and  traces  of  morphia  added,  the 
blue  color  of  iodide  of  starch  appears. 

If  morphia  is  put  into  a  few  drops  of  a  concentrated 
and  slightly  acid  solution  of  a  ferric  salt,  a  beautiful 
blue  color  is  produced,  wliich  subsequently  changes  to 
green. 

Morphia,  moistened  with  nitric  acid,  is  colored 
orange-red,  which  rapidly  changes  to  yellow. 

These  four  reactions  are  chanvcteristic  of  morphia. 

Tf  iodine  and  morphia  are  mixed  in  equal  propor- 
tions and  the  mixture  treated  with  boiling  water,  a 
brown  liquid  is  formed  which  deposits  a  reddish-brown 
jiowder  called  iodomorphia.     Morphia  fused  with  al- 


146 


OKGANIO    CUKMISTKY. 


kalies  yields  niethylamine.  (p.  127).  It  is  attacked  by 
ethyl  iodide  at  100°,  a  single  molecule  of  ethyl 
entering  into  the  group. 

Morphia  forms  crystallizable  salts, from  the  solutions 
of  which  it  is  precipitated  by  the  fixed  alkalies. 

Chlokhydbate  of  moephia,  CnHijNOsHCl+sn^O. 
To  prepare  this  salt,  100  parts  of  pulverized  morphia 
are  treated  with  a  little  warm  water,  then  hydrochloric 
acid  is  added  in  sufficient  quantity  to  dissolve  the  al- 
kaloid. The  solution  is  afterwards  evaporated  in  a 
water  bath  until  it  crystallizes. 

This  salt  is  soluble  in  20  parts  of  cold  water,  very 
soluble  in  alcohol.  It  is  the  salt  of  morphia  most 
used,  and  contains  76  per  cent,  of  morphia. 

Sulphate  op  morphia,  (C„H,oNOs)jH2S04+6H20 
js  prepared  like  the  preceding  salt,  which  it  resembles 
in  appearance  as  well  as  in  properties. 

Moi-phia  and  its  salts  are  used  in  very  small  doses, 
as  in  larger  doses  they  are  energetic  poisons. 

CoDEiA,  CjgllaNOgjIIaO. 

Discovered  in  1832  by  Robiqnet.  This  base,  whose 
name  is  derived  from  x^d^  poppy  head,  exists  in  the 
ammoniacal  solution  obtained  in  the  preparation  of 
morphia.  On  evaporation  the  ammonia  is  driven  off 
and  the  codeia  is  precipitated  by  pot«?sa.  Tlie  codeia 
is  at  first  precipitated  in  the  form  of  a  sticky  mass 
which  soon  becomes  pulverescent.  It  is  washed  with 
and  dissolved  in  hydrochloric  acid.  The  liquid  is  then 
boiled  with  washed  animal  charcoal,  and  the  codeia 
precipitated  with  potassa. 


NABCOTINA. 


14T 


is  attacked  by 
ule  of  ethyl 

the  sohitions 
Ikalies. 
sHCl+SHjO. 
ized  morphia 
hydrochloric 
solve  the  al- 
porated  in  a 

water,  very 
lorphia  most 
a. 
I2SO4+6H2O 

it  resembles 

small  doses, 
as. 


i  base,  whose 
exists  in  the 
eparation  of 
is  driven  off 
The  codeia 
sticky  mass 
tvashed  with 
quid  is  then 
i  the  codeia 


Codeia  is  crystalline,  very  soluble  in  alcohol  and 
ether.  It  dissolves  in  80  parts  of  cold  and  in  20  parts 
of  boiling  water. 

Codeia  is  very  soluble  in  ammonia,  and  nearly  in- 
soluble in  potassa.  With  chlorine,  bromine  and  ni- 
tric acid  it  forms  products  of  substitution.  With 
iodine  it  furnishes  ruby-red  crystals,  whose  formula  ia 

C,8H,iN0aI. 

Codeia  is  somewhat  used  as  an  anodyne.  It  is  easily 
distinguished  from  morphia,  since: 

I.  Codeia  is  soluble  in  ether  and  ammonia. 

II.  It  is  insoluble  in  solutions  of  potassa. 

III.  It  does  not  reduce  iodic  acid  or  feme  salts. 

IV.  Citric  acid  does  not  impart  to  it  any  color. 

NARoariNA,  C22H2SNO7. 

Karcotina  crystallizes  in  rhombic  prisms.  It  is  al- 
most insoluble  in  cold  water,  somewhat  soluble  in 
alcohol,  quite  so  in  etlier.  It  fuses  at  170°,  and  is 
decomposed  before  reaching  200°.  Dilute  nitric  acid 
transforms  it  into  various  products  of  oxydation,  the 
most  important  of  which  are  meconine^  eotarnine 
and  opianio  acid  Narcotina  unites  with  acids,  but 
the  compounds  are  decomposed  on  evaporation. 

It  is  distinguished  from  morphia  in  that  it  does  not 
reduce  iodic  acid  and  ferric  salts,  and  from  codeia  in 
giving  with  nitric  acid  a  blood  red  coloration.  This 
substance  is  also  insoluble  in  potassa  and  ammonia. 
It  is  not  as  poisonous  as  morphia. 


148 


ORGANIC    CHEMISTRY. 


THEBAIA. 

This  alkaloid,  sometimes  called  paramorphia,  is  the 
most  poisonous  of  the  bases  of  opium. 

It  is  crystallizable,  insohible  in  water,  soluble  in 
alcohol  and  ether.  Fuming  nitric  acid  attacks  it  in 
the  cold,  and  a  yellow  liquid  is  obtained,  which  be- 
comes brown  on  contact  with  alkalies,  and  which  dis- 
engages an  alkaline  vapor.  Concentrated  sulphuric 
acid  gives  it  a  red  hue. 

PAPAVERINE. 

This  body  is  crystallizable,  insoluble  in  water,  quite 
soluble  in  boiling  alcohol  and  ether.  It  forms  crystal- 
line salts. 

Under  the  action  of  strong  sulphuric  acid  it  as- 
sumes a  deep  blue  color,  though  Hesse  and  Drag- 
eiidorff  have  recently  ascertained  that  when  absolutely 
pure  no  color  is  obtained,  the  ordinary  article  found 
in  trade  not  being  pure. 


NARCEIA. 

C,3H.«N0b. 

This  alkaloid  crystallizes  in  silky  needles,  insoluble 
in  ether,  soluble  in  alcohol  and  boiling  water,  little 
soluble  in  cold  water.    It  forms  crystallizable  salts. 


OPIUM. 


141^ 


lorphia,  is  the 

er,  soluble  in 
attacks  it  in 
ed,  which  be- 
nd which  dis- 
.ted  sulphuric 


Narceia  fuses  at  96°,  and  commences  to  decompose 
at  about  110°.  It  is  attacked  in  the  cold  by  concentrated 
sulphuric  acid,  a  red  liquid  being  produced  which 
rapidly  becomes  green,  especially  if  slightly  heated. 
The  best  means  of  distinguishing  narceia  is  to  cause  a 
solution  of  iodine  to  act  upon  the  pulverized  substance. 
According  to  Roussin,  the  operation  is  most  easily  per- 
formed with  one  part  of  iodine  and  two  parts  of  potas- 
sium iodide  dissolved  in  ten  parts  of  water.  A  blue 
color  is  produced,  which  disappears  on  coming  in  con- 
tact with  alkalies,  or  on  heating. 


1  water,  quite 
forms  crystal- 

ic  acid  it  as- 
se  and  Drag- 
len  absolutely 
article  found 


lies,  insoluble 
water,  little 
:able  salts. 


PIIYSIOIXKJICAL  ACmON  OF  OPIUM.      NAECXDTIC  POISONS. 

Opium  in  small  doses  is  a  very  highly-prized  ano- 
dyne. Continued  use  of  this  substance  produces  a 
peculiar  state  of  inebriation,  an  excited  sleep  and  hal- 
lucinations of  various  sorts. 

The  bodies  of  ojiium-eaters  are  lean  and  cadaverous^ 
their  eyes  are  lustrous,  their  forms  bent;  their  appe- 
tite diminishes,  and  they  exist  only  by  increasing  the 
dose  of  the  poison  wliich  destroys  them.  In  larger 
doses  it  is  highly  poisonous,  and  acts  in  a  different 
manner  from  that  of  the  poisons  already  studied.  It 
may  be  considered  as  the  type  of  the  narcotic  poisons. 
It  is  not  unfrequently  used  for  criminal  purposes, 
and  the  imprudent  administration  of  laudanum  and 
other  solutions  of  this  substance  often  causes  serious 
effects. 

Claude  Bernard  has  made  a  careful  study  of  the  ac- 
tion of  the  various  alkaloids  ol'  opium  upon  the  system, 


150 


OBOANIO    CHEMISTRY 


and  has  tabulated  their  soporific,  toxic,  and  convulsive 
actions  as  follows : 


Toxic. 

Thebeia, 

Codeia, 

Papaverine, 

Narceia, 

Morphia, 

Karcotina. 


ConTnUlve. 

Thebeia, 

Papaverine, 

^arcotina, 

Codeia, 

Morphia, 

Karceia, 


Soporific. 

Narceia, 
Morphia, 
Codeia. 


With- 

ont 

action. 


Those  at  the  head  of  each  column  are  the  most 
marked  in  the  respective  characteristic  action. 

Subjoined  are  tabulated  the  principal  chemical 
characteristics  of  the  opium  alkaloids  : 


Uorplii*. 

Codeia. 

Narcotina. 
Tliebeia. 

Papaverine. 
Narceia. 


WATIB. 


ALCOHOL. 


Bat  little  sol- 
ubia. 


Soluble. 

Inaolnble. 
Insolnble. 

Insolable. 


Sliglitl 


\j  eorblo 


Quite  lolable. 

Very  soluble. 

Soluble. 
Soluble. 

Soluble. 
Soluble. 


WtBMIL. 


AXMOHIA. 


Almoit    inaol- 
uble. 


Very  soluble 

Soluble. 
Soluble. 

Soluble. 
Inaolable. 


Nearly    insol- 
ublo. 


Soluble. 

Inioluble. 
Insoluble. 

Insoluble. 
Insoluble. 


QUINIA. 


161 


nd  convulsive 


QFINIA   OR  QUININE. 


C»H.«N,0^3HjO. 


Soporific. 

Narceia, 
Morphia, 
Codeia. 


with- 

ont 
action. 


are  tlie  most 

ition. 

>al   chemical 


AXMOHIA. 


Nearly    insol. 
uble. 


Soluble. 

Iniolablei 
Iiuolnble, 

luolable, 


Iniolable. 


!d  in  1820  by  Pelleti'ar 
"a  the  modem  proct 


This  alkaloid  was  "isr 
and  Caventou.    Thr      '!owi> 
by  which  it  is  prepared. 

Yellow  Peruvian  bark  is  carefully  pulverized  and 
thoroughly  mixed  with  30  per  cent,  of  its  weight  of 
lime,  pi-eviously  slacked.  The  mass  is  then  lixiviated 
three  or  four  times  with  refined  petroleum  (petroleum 
ether)  or  amylic  alcohol,  (wood  spirit)  which  dissolves 
the  alkaloids. 


Nearly  inaolnble. 

Insolnblo. 
Ineolnble. 


MrTBIO  ACID. 


BULPBUBIO    ACIV. 


Orange-red    color- 
ation. 


Orani^e-red    color- 
ation, 

Blood -red     color- 
ation. 

Yellow  coloration. 


Colored  violet  on 
heating  with  di- 
late acid. 

Colored  violet  on 
heating  with  di- 
lute acid. 

Tellow  coloration. 

Red  coloration. 

Dark-blae  color- 
ation. 

Red  color,  which 
becomes  green. 


IODIC  ACID. 


Reduced. 

la  not  reduced. 
Is  not  reduced. 


153 


ORGANIC    CHEMISTRY 


The  united  extracts  are  agitated  with  water,  acidu- 
lated with  sulphuric  acid,  making  the  liquid  only 
sh'ghtly  acid. 

When  the  solution  is  completed,  animal  charcoal  is 
added,  and  the  liquid  brought  to  boiling,  filtered  while 
still  hot,  and  allowed  to  cool.  The  quinia  sulphate 
which  is  formed,  2iC.^E^-N^0,),  H^SO^-f  7aq.,  being 
but  slightly  soluble,  is  deposited  on  cooling. 

After  being  allowed  to  stand  24  hours,  the  sulphate 
is  collected,  expressed  and  redissolved  in  as  small  a 
quantity  of  water  as  possible,  containing  a  few  drops 
of  sulphuric  acid. 

The  liquid  on  cooling,  deposits  crystals,  which  are 
dried  at  35°.  The  mother  liquors  are  treated  with 
ammonia,  or  sodium  carbonate,  which  precipitates  a 
certain  quantity  of  the  alkaloid.  The  precipitate  is 
lightly  washed  with  water,  redissolved  in  dilute  sul- 
phuric acid,  boiled  with  washed  animal  charcoal,  and 
allowed  to  cool.  A  second  crop  of  crystals  of  quinia 
sulphate  is  thus  obtained.  The  mother  liquor  contains 
cinchonia  sulphate.  This  sulphate  is  dissolved  in  30 
times  its  weight  of  boiling  water,  allowed  to  cool,  and 
a  slight  excess  of  ammonia  added. 

The  cinchonia  which  is  precipitated  is  collected  on 
a  filter,  and  washed  with  lukewarm  leater  until  the 
filtmte  no  longer  gives  with  barium  chloride  a  white 
precipitate  insoluble  in  acids;  it  is  then  dried  at  a 
temperature  of  30°  to  40°. 

Quinia  is  white,  amorphous  and  very  friable.    It 


I 


SULPHATES   OF   QUINIA. 


153 


I  water,  acidii- 
3  liqaid  only 

lal  charcoal  is 
,  filtered  while 
linia  sulphate 
,-f7aq.,  being 
ng. 

,  the  sulphate 
n  as  small  a 
;  a  few  drops 

Is,  which  are 
treated  with 
)recipltate8  a 
precipitate  is 
n  dilute  sul- 
charcoal,  and 
als  of  quinia 
juor  contains 
(solved  in  30 
[  to  cool,  and 

collected  on 
er  until  the 
iride  a  white 
I  dried  at  a 

friable.    It 


may  be  obtained  in  a  crystalline  condition,  by  adding 
an  excess  of  ammonia  to  a  dilute  solution  of  quinia 
sulphate,  and  allowing  the  solution  to  stand. 

This  crystallized  quinia  melts  at  57",  losing  its  water 
of  crystallization,  solidifies  and  remelts  at  176°.  It 
requires  250  parts  of  boiling  and  460  parts  of  cold 
water  for  its  solution. 

It  dissolves  in  2  parts  of  boiling  absolute  alcohol,  2 
parts  of  chloroform  or  50  to  60  parts  of  ether.  Its 
solutions  are  very  bitter,  levogyrate,  and  for  the  most 
part  .fluorescent. 

Heated  on  platinum  foil,  quinia  swells  up  and  in- 
flames,  leaving  a  deposit  of  carbon.  Heated  with  po- 
tassa  it  produces  hydrogen  and  quinoleine;  (cinchon- 
lein);  it  also  furnishes  a  brown  compound  on  being 
triturated  with  iodine. 

Quinia  is  recognized  by  the  following  reactions.  It 
is  first  saturated  with  very  dilute  sulphuric  acid  and 
chlorine  water;  then  an  excess  of  ammonia  is  added, 
whereupon  a  green  color  is  obtained. 

On  adding  powdered  potassium  ferrocyanide  before 
the  aqua  ammonia  a  rose  coloration  is  produced,  which 
afterwards  becomes  dark  red. 

Quinia  has  a  basic  reaction;  it  forms  with  acids 
crystallizable  salts  from  which  the  alkalies  precipitate 
quinia.  It  is  a  base  which  saturates  two  molecules  of 
a  monobasic  acid. 

ScLPHATKS  OP  Quinia.  Two  sulphates  of  quinia  are 
known;  that  obtained  by  the  process  we  have  above 


154 


OBOANIO   CHEMISTBr. 


described,  is  the  neuti-al  sulphate,  though  generally 
known  as  the  basic  sulphate.     Its  formula  is 

SCjoHmNA-H^SO.+TIIjO. 

This  salt  contains  74.3  per  cent,  of  quinia. 

It  crystallizes  in  very  delicate  needles  l)elongiiig  to 
the  clinorhombic  system,  and  which  effloresce  in  dry 
air.  It  dissolves  in  30  parts  of  boiling  and  740  parts 
of  cold  water;  also  in  60  jmrts  of  cold  absolute  alco- 
hol. It  is  very  nearly  insoluble  in  ether.  Its  solu- 
tions are  extremely  bitter.  It  l)econie8  phosphorescent 
on  l)elng  heated,  and  subseqiiently  fuses. 

Heated  in  the  air  it  burns,  leaving  a  carbonaceous 
residue. 

On  adding  quinia  to  water  acidulated  with  sulphuric 
acid,  it  rapidly  dissolves  and  another  sulphate,  often 
called  the  acid  sulphate,  is  formed,  whose  formula  is 

It  is  on  account  of  the  difficult  solubility  of  the  pre- 
ceding salt,  and  the  great  solubility  of  this  latter  one, 
that  we  cautioned  against  the  employment  of  an  excess 
of  sulphuric  acid  in  the  preparation  of  quinia. 

This  salt  dissolves  in  11  parts  of  water  at  12°,  and 
in  9  parts  at  18°.  Sulphate  of  quinia,  heated  to  130° 
with  acidulated  water  for  several  hours,  is  transformed 
into  an  isomeric  dextrogyrate  base  called  quinieine, 
which  is  likewise  a  febrifuge. 

Medicinal  sulphate  of  quinia  always  contains  sulphate 


QUINIA. 


15t 


^h  generally 


b   IS 


tna. 


)elongiiig  to 
resce  in  dry 
id  740  parts 
)8olnte  alco- 
••  Its  solii- 
•sphorescent 

arbonaceoQs 

tl)  sulphuric 
pliate,  often 
formula  is 


r  of  the  pre- 
8  latter  one, 
of  an  excess 
inia. 

at  12°,  and 

ited  to  130° 

transformed 

quinioine, 

ins  sulphate 


of  cinchonia,  and  its  presence  is  not  considered  fraudu- 
lent, even  when  it  contains  3.5  per  cent,  of  the  latter 
substance,  as  this  salt  is  necessarily  produced  in  the 
preparation  of  quinla.  Cinchonia  appears  to  be  of  Uttle 
therapeutic  value,  and  is  often  added  to  sulphate  of 
quinia. 

This  adulterant  is  detected  by  weighing  out  0.5 
grams  of  the  salt,  and  adding  to  it  5  grams  of  ether 
The  mixture  is  agitated  and  1.5  grams  of  concentrated 
ammonia  added.  If  no  cinchonia  is  present,  two  liquid 
layers  are  obtained  ;  if  it  is  present,  a  layer  of  this  al- 
kaloid is  formed  directly  above  the  ammonia.  Good 
commercial  sulphate  of  quinia  should  give  only  a  very 
thin  layer.  ^ 

The  amount  of  quinia  may  be  directly  determined 
by  decanting  and  evaporating  the  ethereal  solution 
and  weighing  the  residue.  This  result  may  be  verified 
by  replacmg  the  ether  in  another  determination,  by 
chloroform,  wliich  dissolves  both  bases;  the  residue 
obtained  by  the  evaporation  of  this  liquid  furnishes  the 
weight  of  the  quinia  and  cinchonia  together. 

Sulphate  of  quinia  sometimes  contains  sulphate  of 
quinidia;  this  base  is  precipitated,  together  with  cin- 
chonia, by  ether.  Its  presence  may  be  detected  by 
dissolving  one  gram  of  the  sulphate  in  30  grams  of 
boihng  water,  and  adding  to  the  solution  ammonium 
oxalate.  Oxalate  of  quinidia,  which  is  the  only  soluble 
oxalate  of  these  bases,  remains  in  solution,  and,  on  fil- 
tering, a  bitter  liquid  will  be  obtained,  in  which  the 
quinidia  may  be  precipitated  by  ammonia. 


156 


OROANIO   CHEMISTRY. 


In  case  sulphate  of  quinia  has  been  adulterated  with 
calcium  sulphate,  or  other  inorganic  substance,  it  may 
be  recognized  by  a  residue  which  will  be  obtained  on 
heating  the  sulphate  to  redness  on  platinum  foil. 

Sulphate  of  quinia  sljouid  dissolve  in  80  per  cent, 
alcohol.  If  it  dissolves  in  water,  but  does  not  dissolve 
in  r.6  per  cent,  to  60  per  cent,  alcohol,  it  may  be  re- 
garded as  not  pure. 

If  adulterated  with  starch,  or  fatty  bodies,  a  clear 
solution  cannot  be  obtained,  even  in  very  large  quanti- 
ties of  water. 

Should  it  contain  sugar  it  will  emit  an  odor  of 
caramel  on  ignition,  and  blacken  in  contact  with  sul- 
phuric acid. 

Quinia  sulphate  to  which  salicin,  a  common  adulter- 
ant, has  I  Jen  added,  is  colored  red  by  sulphuric 
acid. 

Quinia  sulphate  is  chiefly  employed  in  cases  of  in- 
termittent fevers. 

CINCHONIA  OB   CINCHONINE. 


.    CaoIIaiNjO. 

Cinchoniawas  discovered  by  Duncan  in  1803,  though 
first  recognized  as  an  oiganic  base  by  Pelletier  and 
Caventou  in  1820. 

It  differs  from  quinia  in  containing  one  atom  less  of 
oxygen  ;  it  has  never  been  converted  into  quinia. 

It  is  prepared  in  the  same  manner  as  quinia,  but 


:erated  with 
mce,  it  may 
)btained  on 
Ti  foil. 
iO  per  cent, 
not  dissolve 
may  be  re- 
lies, a  clear 
irge  quanti- 

an  odor  of 
3t  with  sul- 

lon  adnlter- 
'   sulphuric 

iases  of  in- 


303,  though 
jlletier  and 

item  less  of 
[uinia. 
qninia,  but 


CINCHONIA. 


167 


from  the  Gray  Peruvian  Bark.  Ciiichonia  separates 
out  in  crystals  on  the  evaporation  of  the  alcohol  with 
wiiich  the  calcic  precipitate  is  M'ashed. 

The  crystjils  of  cinchonia  are  collected,  allowed  to 
drain,  and  the  liquid  which  runs  off  will  furnish  addi- 
tional crystals  on  being  evaporated.  To  this  mother 
liquor  sulphuric  acid  is  added  in  excess,  and  the  solu- 
tion slightly  evaporated. 

The  first  crystals  obtained  are  sulphate  of  qt  nia, 
which  is  leas  soluble  than  sulphate  of  cinchonia. 
When  nothing  remains  but  a  very  concentrated  mother- 
liquor,  the  cinchonia  is  precipitated  by  ammonia,  a.d 
freed  from  quinia  by  washing  with  ether.  The  quinia 
dissolves,  while  the  cinchonia  remains  insoluble. 

The  latter  crystallizes  in  brilliant  colorless  crystals, 
which  are  insoluble  in  cold  water  and  ether,  soluble  in 
2,500  parts  of  boiling  water,  in  30  parts  of  boiling  90 
per  cent,  alcohol,  and  40  parts  of  chloroform. 

Its  solutions  are  very  bitter  and  dextrogyrate. 
Cinchonia  melts   at  about  257°;   on  heating  to  a 
slightly  higher  temperature  in  a  current  of  nitrogen, 
or  hydrogen,  it  is  completely  sublimed. 

"With  chlorine  and  bromine,  it  furnishes  dichloride 
and  dibromide  of  cinchonia.  With  iodine,  a  yel- 
low crystalline  body  is  obtained,  whose  formula  is 

Heated  with  fused  potassa,  it  produces  qumoleine. 

Cinchonia  has  an  alkaline  reaction.  It  ur»'  j>  rith 
acids,  forming  salts  which  correspond  to  the  suits  of 
quinia,  though  generally  more  soluble. 


158 


ORGANIC    CHEMISTRY. 


Cinchonia  sulphate,  heated  to  about  136°,  furnishes 
the  sulphate  of  an  isomeric  alkaloid,  cinchonieia  or 
cinchonicine. 

Cinchonia  is  employed  as  a  febrifuge  in  Holland,  and 
a  few  other  countries,  but  its  action  is  regarded  as  in- 
ferior to  that  of  quinia. 

QuiNoiDiNE.— ^?/mw?«a  is  a  base  obtained  from  the 
last  mother-liquor  in  the  preparation  of  quinia,  by 
precipitation  with  sodium  carbonate.  It  is  olten  min- 
gled with  another  alkaloid,  cinohonidia  or  cinchoni- 
dine,  and  it  is  this  mixture,  containing  chiefly  quinidia, 
which  is  called  quinoidlne  in  commerce. 

Quinidia  is  isomeric  with  quinia;  it  melts  at  160". 
It  is  difiicultly  soluble  in  water,  very  soluble  in  boil- 
ing alcohol,  and  slightly  soluble  in  ether.  Its  solutions 
are  dextrogyrate.  Quinidia  acts  as  a  iebrifnge.  With 
chlorine  and  ammonia,  it  gives  the  same  reactions  as 
quinia,  and  forms  corresponding  salts. 

Quinoidlne  contains,  as  we  have  said,  cinchonidia,  a 
substance  isomeric  with  cinchonia.  This  body  is  crys- 
talline, fusible  at  about  150°,  almost  insoluble  in  water, 
slightly  soluble  in  ether  and  chloroform ;  boiling  alco- 
hol is  the  best  solvent  for  cinchonidia. 


STKYOJINIA. 


159 


^36°,  furnishes 
inchonieia  or 


Holland,  and 
egarded  as  in- 

iiied  from  the 
of  quinia,  by 
t  is  otten  min- 
or cinohoni- 
iefly  quinidia, 

melts  at  160". 
uble  in  boil- 
Its  solutions 
ifnge.  With 
!  reactions  tis 


inchonidia,  a 

body  is  crys- 

ible  in  water, 

boiling  alco- 


ALKALOIDS  OF  THE  STRYCHNOS. 

The  two  chief  alkaloids  are  strychnia  and  brucia. 
Desnoix  extracted  from  the  nux  vomica  another  alka- 
loid, which  he  named  igasuria;  but  according  to 
Schutzenberger,  this  body  is  a  mixture  of  several 
bases. 

Tliese  alkaloids  are  extracted  from  the  fruit  of  the 
Strychnos  nux  vomica  ;  from  St.  Ignatius'  beans,  fruit 
of  the  Strychnoa  Ignatii ;  from  the  wood  of  Coulevre, 
root  of  the  Sirychn^s  eoluhrina  ;  from  the  upas,  the 
poison  of  indi'an  arrows,  extracted  from  the  Strychnoa 
tieute;  from  the  False  Angiistura  Bark,  and  the  bark 
of  the  Strychnoa  nux  vomica,  which  contains  princi- 
pally brucia. 

KTRYOHNIA. 

C,,II.^NA. 

Nux  vomica  is  pulverized  and  boiled  with  three  suc- 
cessive portions  of  water  containing  sulphuric  acid,  and 
these  decoctions  evaporated  in  a  water  bath.  When 
the  liquid  is  reduced  to  a  small  volume,  126  grams  ot 
quicklime  slacked  to  a  thin  paste  are  added  for  each 


160 


OKQANIO    CHEMISTRY. 


kilo,  of  mix  vomica.  The  precipitate  is  collected  on  a 
cloth,  waslied,  dried,  and  treated  with  90  per  cent,  al- 
cohol. 

The  alcoholic  solution  is  distilled  to  three-fourths  its 
volume  and  left  to  crystallize.  The  crystals  obtained 
are  chiefly  strychnia  ;  these  are  allowed  to  drain,  then 
dissolved  in  water  containing  ^  its  weight  of  nitric 
acid,  and  the  sohuion  concentrated  in  a  water  bath. 

The  nitrate  of  brucia  remains  dissolved  and  the 
nitrate  of  strychnia  crystallizes  ont.  These  crystals 
are  re^lissolved  in  water,  animal  charcoal  added,  the 
solution  brought  to  boiling  and  then  filtered. 

Ammonia  is  added  to  tins  liquid,  the  precipitate 
washed,  dried,  and  dissolved  in  boiling  alcohol,  which 
deposits  the  alkaloids  on  cooling. 

This  method  is  at  present  very  advantageously  sup- 
planted  by  the  process  given  for  the  production  of 
quinia,  which,  briefly  stated, consists  in  treating  the  sub- 
stance  with  lime  directly  and  employing  a  solvent  for 
the  alkaloids,  which  is  insoluble  in  water,  such  as  petro- 
leum or  amylic  alcohol. 

Strychnia  crystallizes  in  octahedrons  or  in  prisms  of 
the  rhombic  system;  they  are  colorless,  very  bitter, and 
almost  insoluble  in  water  or  ether,  but  readily  soluble 
in  ordinary  alcohol  diluted  with  15  per  cent,  of  water. 
Strychnia  treated  with  potassa  furnishes  a  small  qnan- 
ti  ty  of  quinoleine.  lod  ide  of  ethyl  produces  wi  th  this 
base  the  cx)inpound 


BBUOIA 


161 


sollected  on  a 
per  cent,  al- 

Be-fonrths  its 
tals  obtained 

0  drain,  then 
?lit  of  nitric 
ater  bath, 
v^ed  and  the 
lese  crystals 

1  added,  the 
ed. 

I  precipitate 
johol,  which 

^ously  snp- 
•oduction  of 
tingtliesub. 
I  solvent  for 
ich  as  petro- 

in  prisms  of 
y  bitter,  and 
idily  soluble 
it.  of  water, 
small  qnan- 
es  with  this 


CaHa(CjH5)NaOJ. 

Chlorine  gas  renders  even  a  dilute  solution  of  this 
alkaloid  turbid  and  the  liquid  becomes  acid;  this 
reaction  is  characteristic.  Bromine  also  forms  deri- 
vatives by  substitution.  Iodine  combines  directly  with 
the  molecule  of  strychnia. 

Strychnia  dissolves  in  strong  sulphuric  acid;  the  so- 
lution is  colorless  and  becomes  dark  blue  in  contact 
M'ith  potassium  bichromate  or  lead  dioxide.  The 
color  rapidly  passes  to  red  and  finally  to  a  yellow. 

Strychnia  is  colored  yellow  by  hydrogen  nitrate 
only  when  it  contains  brucia,  a  trace  of  which  is  suf- 
ficient to  produce  the  change. 

Strychnia  forms  with  acids  crystallizuble  salts. 
Tlie  nitrate  CaJIcNA.HNOs  crystallizes  in  fine 
needles \cry  soluble  in  hot  water. 

Strychnia  is  among  the  most  powerful  poisons,  2  to 
3  centigrams  being  sufficient  to  canee  death.  There  is 
believed  to  be  no  reliable  antidote  for  strychnia  though 
F.  M.  Peirce  claims  that  small  doses  of  prussic  acid 
are  efiicient  for  the  purpose.     (44-'68-336.) 

BEUCI.V. 

Ca3H»IfA,4n,0. 

To  obtain  this  alkaloid  the  alcoholic  liquids  from 
which  strychnia  has  been  i-emoved,  are  saturated  with 
oxalic  acid  and  evaporated.  The  crystals  of  oxal- 
Ate  of  brucia  which  are  formed,  are  washed  with  95  per 


163 


ORGANIC    CHEMISTRY. 


cent,  alcohol  and  redissolved  in  water.  The  solution 
is  decomposed  by  lime,  the  precipitate  collected,  dried 
and  dissolved  in  boilujof  alcohol;  brucia  then  crystal- 
lizes out  and  is  purified  by  two  recrystallizations. 

Crystals  of  brucia  are  large  and  of  the  clinorhombic 
system;  they  are  solnble  in  alcohol,  insoluble  in  ether, 
but  soluble  in  850  parts  of  cold,  or  600  parts  of  boil- 
ing  water. 

Concentrated  sulphuric  acid  strikes  a  rose  color  with 
brucia  which  afterwards  changes  to  green.  ]Sitric  acid 
colors  it  red,  and  if  heated  it  gives  off  nitrous  ether, 
methyl  alcohol  and  carbon  dioxide. 
Brucia  is  much  less  poisonous  than  strychnia. 
It  may  be  distinguished  from  strychnia  by  its  reac- 
tion with  nitric  acid.  A  red  color  is  produced  by 
brucia,  which  passes  to  violet  on  the  addition  of 
stannous  chloride.  This  latter  coloration  does 
not  take  place  with  morphia.  Brucia  is  also  one  of  the 
best  reagents  for  nitric  acid. 

CcKAEiNA.— From  the  arrows  of  the  Indians  living 
on  the  shores  of  the  Amazon  and  Orinoco,  a  brown 
resinous  matter  is  collected,  from  which  ciystais  of  a 
substance  have  been  obtained  whose  poisonous  action 
is  exceedingly  rapid.  Preyer,  to  whom  we  owe  this 
discovery,  regards  its  formula  as  C.oHjsN,  and  has 
named  it  curarina. 

Tlie  Indians  of  Dutch  Guiana  poison  their  arrows 
with  two  other  substances  no  less  dangerous:  tirari 
and  tikunm.  These  three  substances  paralyze  the  ac- 
tion of  the  muscles  by  destroying  the  motor  nerves 


VKRATRIA. 


163 


Tlie  Bolution 
llected,  dried 
then  crystal- 
sations. 
jlinorhombic 
ible  in  ether, 
parts  of  boil- 

86  color  with 

^  itric  acid 

itroua  ether, 

chnia. 
by  its  reac- 
produccd  by 
addition  of 
ation  does 
30  one  of  the 

dians  b'ving 
CO,  a  brown 
I'ystais  of  a 
tions  action 
'6  owe  tills 
^,   and  has 

icir  arrows 
oils:  tirari 
lyze  the  ac- 
►tor  nerves- 


(Claude  Bernard).  It  appears  that  urari,  though  a  fa- 
tal poison  when  introduced  into  the  blood  by  a  wound, 
may  yet  be  swallowed  with  impunity. 

DEASnO   POISONS. 

We  shall  not  describe  the  preparation  of  the  follow- 
ing alkaloids,  on  account  of  their  minor  importance. 
The  process  in  general  is  similar  to  tliat  by  which  the 
preceding  ones  are  prepared:  The  alkaloid  is  dissolved 
in  an  inorganic  acid,  precipitated  by  a  base,  and  redis- 
solved  in  an  appropriate  solvent. 

The  roots  of  the  white  hellebore  ( Veratrum  album) 
and  its  seeds,  furnish  an  alkaloid  called  veratria^ 
C32H53N2O8.  It  crystallizes  in  prisms  having  a  rhom- 
bic base.  Tliey  are  very  bitter,  insoluble  in  water, 
soluble  in  alcohol  and  ether,  and  melt  at  115°.  Yera- 
tria  is  dissolved  by  strong  nitric  acid,  the  solution  be- 
ing violet  Sulphuric  acid  colors  it  first  yellow,  then 
red. 

Three  other  poisonous  bases,  mhadilUa^  eolchinia, 

and  jervia,  are  found  ass«jciated  with  veratria  in  the 

Veratrum    album.    Jervia,    C,>oHj8N2032H2(),    (Ger- 

hardt  and  Wills'  analysis)  is  white,  crystalline  and 

fusible. 

These  bodies  are  very  corrosive  poisons,  producing 
great  irritation  of  the  alimentary  canal, 

ALKALOIDS  OF  THE    rOISONOUS    SOLANACK.K. 

The  belladona,  Atropa  belladona,  and  the  thorn- 
apple,  i^a^ura  «<m/tto/i<wn,  furnish  each  an  alkaloid 


164 


ORGANIC    CHEMISTRY. 


called,  respectively,  atropia  and  daturia,  the  formula 
of  which  is  CnllasNOs. 

This  substance  cijstallizes  in  fine  needles,  which  are 
fusible  at  about  90°,  and  are  partially  sublimed  at 
about  135°.  It  is  difficultly  soluble  in  water,  bnt  very 
soluble  in  alcohol  and  ether. 

Heated  with  an  oxydiziiig  agent,  such  as  potassium 
bichromate,  or  sulphuric  add,  it  disengages  essence  of 
bitter  almonds,  easily  recognizable  by  its  odor,  and 
crystals  of  benzoic  acid  are  sublimed.  With  sulphuric 
acid  a  violet  color  is  produced,  accompanied  by  a  frar 
grant  odor  resembling  that  of  a  rose. 

Hydrochloric  acid  furnishes  two  acids  with  atropia, 
tropic  CaHroOs,  and  atropio  CsTlaOj. 

Cases  of  poisoning  by  atropia  are  rare,  but  instances 
m  which  persons  are  poisoned  by  the  berries  of  bella- 
dona  are  of  frequent  occurrence. 

The  black  henbane,  Byosoiamita  niger^  furnishes 
silky  needles  of  a  substance,  hyosciamine,  whicli  has 
much  resemblance  to  atropia,  but  whose  action  as  a 
poison  appears  to  be  less  violent. 

Its  physiological  action  is  on  the  nerves  rather  than 
on  the  muscles.  It  causes  less  dilation  of  the  pupil  of 
the  eye,  and  produces  a  sombre  delirium. 

Belladona  and  atropia,  the  datura,  the  henbane  and 
hyosciamine,  as  well  as  the  poisonous  solanacea  in 
general,  should  be  classed  among  the  narcotic  poisons. 
Poisoning  produced  by  belladona,  and  by  most  of 
the  poisonous  solanaceas,  is  characterized  by  great  dila- 
tion of  the  pupils  of  the  eyes.     The  patient  is  also 


ACONITINA. 


d,  the  formula 

iles,  which  are 
y  sublimed  at 
ater,  bntvery 

1  as  potassium 
ges  essence  of 
its  odor,  and 
rith  sulphuric 
nied  by  a  frar 

with  atropia, 

but  instances 
rries  of  bella- 

'<?/•,  furnishes 
le,  whicli  has 
B  action  as  a 

8  rather  than 
the  pupil  of 

henbane  and 
solanacese  in 
jotic  poisons. 
I  hy  most  of 
)y  great  dila- 
tieut  is  also 


165 


seized  with  vertigo  and  strange  hallucinations  followed 
by  a  turbulent  delirium  and  convulsions.  The  face  is 
congested,  respiration  ditticult,  and  the  skin  often 
breaks  out  in  an  eruption  similar  to  that  iu  rubeola 
(measles). 

No  antidote  is  known  for  these  poisons;  an  infusion 
of  unroasted  coft'ee.  tea,  or  other  astringent  substances 
is  recommended,  but  the  use  of  energetic  emetics  and 
pni'gatives  is  the  most  efficient  method  or  treatment. 

The  chemical  chai'acters  of  these  alkaloids  has  not 
been  as  yet  very  fully  studied. 

Desfosse  has  extracted  from  the  woody  nightshade, 
Solatium  dulcamara,  from  the  berries  of  the  felon- 
wort  and  from  the  young  sprouts  of  the  potato,  /Sola- 
numttthero8um,a  substance  called  solanine,  O^sHnNOig, 
a  highly  poisonous  alkaloid.  On  being  boiled  with 
acids,  it  furnishes  a  stronger  base  solanidine  and 


glucose. 


ACONmNA. 


Aconitina  is  extracted  from  the  monk's-hood, 
Aoonitum  napellus,  as  a  colorless  amorphous,  bitter 
powder,  soluble  in  alcohol,  slightly  soluble  in  ether,  and 
almost  insoluble  in  water.  It  fuses  at  120°,  and  is  al- 
kaline. It  is  a  very  active  poison.  Planta  gives  its 
formula  aa  08oH4.Nb,  ( O- 

Duquesnel  has  extracted  from  the  Aoonitum  napel- 
lu8  a  crystalline  alkaloid,  whose  formula  is  CjjH^NO. 


166 


ORGANIC     CHEMISTRY. 


DIGITALIN. 

This  substance  was  long  ago  obtained  in  an  amor- 
phous condition  from  the  purple  fox-glove.  In  1871 
Kativelle  succeeded  in  obtaining  it  in  a  crystalline 
form.  An  extract  of  fox-glove  is  first  prepared,  con- 
centrated by  distillation  and  dilluted  with  3  times  its 
volume  of  water. 

A  precipitate  is  formed  which  contains  two  bodies 
diftalin  and  digitin.  Tl.is  deposit,  washed  with' 
boihng  alcohol,  furnishes  crystals  composed  of  these 
two  substances,  which  are  easily  separated  by  chloro- 
form, as  digitalin  is  dissolved  by  it  in  all  proportions, 
whiledigitin  is  insoluble. 

Th«  proportion  of  digitalin  in  Digitalin  grown  in 
difterent  countries,  has  been  made  the  subject  of 
special  investigation  by  Prof.  S.  P.  Duffield,  of 
Detroit.    (94-1868.) 

Digitalin  is  very  bitter  to  the  taste.  It  powerfully 
iiTitates  the  nostrils,  and  is  an  active  poison.  If  digi- 
tahn  be  moistened  with  strong  sulphuric  acid  and  then 
exposed  to  the  vapors  of  bromine,  it  assumes  a  purple 
color,  which  is  darker  or  lighter  according  to  the  pro- 
portions employed.  Hydrochloric  acid  produces  with 
digitalin  a  very  intense  emerald  green  color. 

One-fonrth  of  a  milligram  is  sufficient  to  produce 
the  ordinary  poisonous  effects  ot  digitalis.  A  milli- 
gram produces,  in  from  three  to  five  days,  a  marked 
change  in  the  circulation.  Three  milligrams  produce 
most  dangerous  effects  within  24  hours. 


d  in  an  amor- 
>ve.  In  1871 
a  crystalline 
repared,  con- 
th  3  times  its 

8  two  bodies, 
washed  wilh 
>sed  of  these 
3d  by  chloro- 
proportions, 

lia  grown  in 

9  subject  of 
Duffield,    of 

t  powerfully 
on.  If  digi- 
Lcid  and  then 
nes  a  purple 
'  to  the  pro- 
oduces  with 
)r. 

to  produce 
I.  A  niiHi- 
B,  a  marked 
ms  produce 


EMETIA. 


167 


It  ie  much  to  be  desired  that  physicians  substitute 
this  crystalline  substance,  which  is  invariable,  for  the 
amorphous  digitalin,  which  varies  greatly,  both  as  to 
character  and  effectiveness.  Tardieu  places  digitalin 
among  the  hyposthenic  poisons. 

Poisoning  by  digitalin  has  often  been  produced 
through  imprudence. 

The  npm  antinr,  with  which  the  Indians  poison 
their  arrows,  is  obtained  from  the  Antiaria  toxicaria. 

EMEtlA. 

This  body  is  obtained  from  the  roots  of  the  ipecac- 
uanha, Cephcsles  ipecacuanhxi;  it  also  exists  in  the 
Richardsonia  brasiliensia,  in  the  Phaychtria  emetica^ 
and  in  the  roots  of  the  Cainca  (madder  tribe).  These 
materials,  reduced  to  a  nowder,  are  treated  with  con- 
centrated  alcohol,  and  the  alcohol  then  distilled  off. 
The  extract  is  diluted  with  five  times  its  volume  of 
water,  and  filtered.  To  the  filtrate  2  per  cent,  of 
caustic  potassa  i-  added,  and  this  mixture  agitated 
with  chloroform.  The  chloroform  is  decanted  and 
distilled  ;  the  emetia  crystallizes  out.  It  is  dissolved 
in  dilute  sulphuric  acid,  and  precipitated  from  the  so- 
lution with  ammonia.  A.  Glenward  (105 -[3]  6—201) 
gives  CisHijjNOa  as  the  formula  of  emetia. 

It  is  amorphous,  yellowish,  fusible  at  50",  soluble 
in  water  and  alcohol.  Its  solutions  are  slightly  bitter. 
It  is  a  very  weak  base,  and  its  salts  are  not  crystalline. 
A  few  centigrams  suffice  to  produce  vomiting. 


168 


ORGANIC    CHEMISTHY. 


f       ■' 


CANTJIARIDIN 

is  a  very  poisono.is  crybtalline  substance,  obtained  from 
bpamsh  flies,  {Lylta  veslcatoria,  and  other  varieties) 
and  has  tbe  compo.«ition  CHA-  It  is  present  in 
nearly  all  parts  of  the  flies,  va.-ying  in  amount  from  0  5 
to  1.2  per  ce,.t.  R  AVolff  has  of  late  given  this  sub- 
stance a  very  full  investigation.     (95,  May,  '77-102.) 

CAFFEINE  (cAFFEIa)  OB  THEINE  (thEIa). 

C8HioN,02,H20. 

Alcohol  is  added  to  a  mixture  of  5  parts  coflTee  and 
1  part  slacked  lime,  until  nothing  further  is  dissolved, 
and  the  solution  distilled.  The  residue  is  treated 
with  water,  which  causes  an  oil  to  separate  out 
The  watery  liquid  fnrnishes  crystals  which  are  puri- 
faed  by  treating  with  animal  chai-coal,  and  recrystal- 
lizing  in  hot  water. 

The  extractive  matters  of  the  Jcolamut  and  mate  pos- 
sess the  same  properties  as  caffeine. 

Caffeine  crystallizes  in  flue  needles,  fusible  at  178° 
and  is  volatile  at  a  slightly  higher  temperature.   These 
crystals  are  but  little  soluble  in  ether  and  cold  water 
yet  dissolve  very  readily  in  alcohol  and  boiling  water! 

It  IS  remarkal)le  that  the  instinct  of  man  should 
have  led  hmi  to  select,  as  tl;e  bases  of  common  bever- 
'Jges,  just  the  four  or  five  plants,  which  out'  of  many 
thousands  are  the  only  ones,  as  far  as  we  know,  con- 
taining  caffeine. 


THEOBROMINE. 


1G9 


►btained  from 
ber  varieties) 
is  preseHt  in 
mnt  from  0.5 
en  this  6ub- 
7,  '77-102.) 

eia). 


ts  coffee  and 
is  dissolved, 
5  is  treated 
jparate  out 
;h  are  pnri- 
d  recrystal- 

id  mate  pos- 

)le  at  178°, 
ture.  These 
cold  water, 
iling  water, 
nan  should 
inon  bever- 
it  of  many 
know,  con- 


It  is  recognized  b^'  boiling  with  fuming  nitric  acid ;  a 
yellow  li(juid  is  produced.  On  being  evaporated  to 
dryness,  and  ammonia  added  to  the  residue,  a  purplo 
coloration  is  produced,  i-esenibling  murexide,  (p.  125.) 
Amallo  acid  and  CholestropJMn  are  jiroducts  of  the 
action  of  oxidizing  agents  u])on  caffeine;  bodies  dik- 
ing this  alkaloid  to  the  uric  acid  group. 

THEOBKOMINE. 

There  is  extracted  from  th.e  caco,  Theohroina  cacao,  a 
principle  crystallizing  in  microscopic  crystals,  volatile 
at  295°,  soluble  in  alcohol  and  ether,  and  slightly  so  in 
water.  It  furnishes  salts  which  are  decomposed  by 
water.     It  is  called  theohromine',  its  formula  is  CIL 

PICBOTOXIN. 

CsHsO,. 

From  the  Indian  berry,  Cocculus  Indieits,  there  is 
extracted  a  white  crystalline  matter  of  extreme  bitter- 
ness, called  piGrotoxin,  {fvom  Tttxfx'n  bitter  roHixhv.) 
This  body  is  neutral,  difficultly  soluble  in  water,  and 
easily  soluble  in  alcohol  and  ether;  its  solutions  are 
levogyrate. 

The  physiological  action  of  picrotoxin  is  analo- 
gous to  that  of  strychnia,  but  it  differs  from  it  in  that 
it  renders  the  action  of  the  heart  slower,  and  produces 
vomiting. 

Prof.  J.  W.  Langley,  of  Pittsburg,  has  contributed 


1 


170 


OKGANIO   CHEMI8TUV. 


much  to    (87-1862)   our  knowledge  of  the  chemical 
character  of  picrotoxin. 

POLTATDMIO  ALKALOIDS. 

Iliei-e  are  polyatomic  bases  which  are  to  the  mona- 
tomic  bases  what  polyatomic  alcohols  are  to  monatomic 
alcohols. 

They  are  built  upon  the  type  of  several  molecules 
of  ammonia,  or  condensed  ammoniii,  in  the  same  man- 
ner that  polyatomic  acids  and  alcohols  are  derived 
from  several  molecules  of  water. 

Cloez  obtained  the  former  by  the  action  of  ethylene 
bromide  upon  potassa  dissolved  in  alcohol. 

Hoffmaim  established  their  true  formula.  They  are 
called  polyaminea. 

EXAMPLE. 


Ethylenic  diamine,  K, 


Diethylenic      " 


Triethylenic 


(     H, 


^. 


C2H4 


UREA. 


0H4NjO=]^„ 


POLYATOMIC    ALKALOIDS 


171 


the  chemical 


to  the  mona- 
:o  monatomic 

al  molecnies 
e  same  man- 
are  derived 

I  of  ethylene 

I.    They  are 


Eonelle,  Jr.,  was  the  first  to  obtain  this  body  in  an 
impure  state  from  urine. 
Fourcroy  and  Vanquelin  first  obtained  it  pure. 
Woehler,  in  1828,  prepared  it  artificially  by  a  remark- 
able synthesis,  the  first  attempt  to  form  a  body  syn- 
thetically. Urea  forms  the  chief  constituent  of  the 
urine  of  mammalia,  amounting  to  nearly  one-half  of  the 
solid  constituent;  a  small  proportion  of  urea  is  found 
in  all  the  fluids  of  the  body. 

It  is  an  excretory  product,  as  the  hydrogen  and 
carbon  which  have  taken  their  part  in  the  body,  escape 
mainly  in  the  form  of  water  and  carbon  dioxide,  so 
the  nitrogen  is  eliminated  from  the  system  chiefly  in 
the  form  of  urea^ 

Urea  may  be  extracted  from  urine  by  evaporating 
this  liquid  to  one-tenth  its  volume  and  adding,  after  it 
has  become  cold,  an  excess  of  nitric  acid.     Brown 
crystals  of  nitrate  of  urea  are  formed:  these  are  drain- 
ed, expressed,  resiissolved  in  water  and  boiled  with 
animal  charcoal.     This  solution  is  filtered,  and  on 
evaporation  it  deposits  crystals  of  nitrate  of  urea. 
This  salt  is  then  dissolved  in  as  small  a  quantity  of 
water  as  possible,  and  the  solution  treated  first  with 
barium  carbonate,  then  with  a  strong  solution  of  potas- 
Slum  carbonate;  urea  is  set  free  and  barium  and  potas- 
smm  nitrates  formed.     The  above  mentioned  salts  are 
added  as  long  as  efifervescence  is  produced;  the  liquid 
IS  then  evaporated  to  dryness,  and  the  residue  treated 
with  absolute  alcohol,  which  dissolves  only  the  urea 
(J.  E.  Loughlin,  100-5-362.) 


172 


ORGANIC     CHEMISTRY 


The  synthetic  method  employed  by  "Woeliler,  con- 
sists in  preparing  cyanate  of  ammonia,  which  body  is 
isomeric  with  urea. 

Cyanate  of  Ammonium=H4CN20=NH4-Q-CN. 

This  substance  changes  spontaneously  into  urea. 

Heat,  upon  an  earthen  plate,  28  parts  of  potassium 
ferrocyanide  and  14  parts  of  manganese  dioxide,  both 
finely  pulverized,  and  dry  until  the  mixture  becomes 
pasty;  when  cold,  the  mass  is  pulverized  and  ti^eated 
with  water,  and  20  parts  of  ammonium  sulphide  added 
to  the  liquid,  which  is  now  evaporated  in  a  water  bath, 
and  the  residue  treated  with  boiling  alcohol.  On 
evaporating  the  alcoholic  solution,  crystals  of  urea  are 
deposited.  Urea  is  also  obtained  as  a  product  of  other 
reactions.  It  crystallizes  in  prisms  of  the  tetragonal 
system;  these  crystals  are  colorless,  without  odor,  and 
have  a  cooling  taste. 

It  is  soluble  in  its  own  weight  of  water  at  15",  in  an 
equal  weight  of  boiling  alcohol,  and  in  5  parts  of  cold 
80  per  cent,  alcohol ;  it  is  difiicaltly  soluble  in  ether. 
Its  solutions  are  neutral. 

Urea  fuses  at  120";  at  about  160°  it  is  decomuosed, 
yielding  ammonium  carbonate,  ammdidef  CaOHgNj, 
and  biuret,  CjOaHsNj. 

■  Oxydizing  agents  decompose  urea.  Chlorine  also 
decomposes  solutions  of  urea  in  the  following  man- 
ner: 

3Cla  +  HaO  +  CH4NaO=6HCl+Na  +  C08 . 

Urea  heated  to  140°  with  water  in  scaled  tubes,  is 
transformed  into  ammonia  and  carbon  dioxidf: 


UREA. 


178 


Woeliler,  con- 
wliich  body  is 

■  into  urea. 
s  of  potassium 
dioxide,  both 
xture  becomes 
d  and  ti^ated 
•ulphide  added 
1  a  water  bath, 
alcohol.  On 
als  of  urea  are 
oduct  of  other 
;he  tetragonal 
lOut  odor,  and 


H2O + CH4N20=C03 + 2NPL 


This  transformation  likewise  occurs  when  urea  is 
heated  with  strong  sulphuric  acid,  or  fused  with  po- 
tassa,  also,  spontaneously,  in  presence  of  the  nitro- 
genous matters  of  the  urine. 

Urea  does  not  appear  to  unite  with  all  acids.  It  has 
not  yet  been  combined  with  carbonic,  chloric,  lactic  or 
uric  acids.  The  nitrate,  chloride  and  oxalate  of  urea 
are  crystalline. 

Urea  forms  combinations  with  mercury,  silver, 
and  sodium  oxides,  also  with  mercuric  and  silver 
nitrates,  etc. 


rat  15°,  in  an 

parts  of  cold 

ible  in  ether. 

decomposed, 
le,  CsOHsN,, 

Chlorine  also 
lowing  man- 

fCOj. 

lied  tubes,  is 
oxidf; 


I 


174 


ORGANIC   CHEMISTBY. 


NATURAL  FAT8  AN^D  OILS. 

Tlie  fatty  bodies  are  very  widely  distributed  through- 
out the  vegetable  and  animal  Hngdoms.  Some  are 
liquid,  others  are  more  or  less  solid.  Certain  oils  re- 
main liquid  exposed  to  the  air,  as  olive  oil;  others 
oxydize  and  thicken,  as  linseed  oil,  poppy  oil,  and 
nut  oils;  the  latter  are  called  negative  oils,  and  are 
nsed  in  the  manufacture  of  varnishes,  printers'  ink, 
oil  cloth,  also  in  paints. 

Fats  and  oils  are  insoluble  in  water;  thev  are  among 
the  very  few  bodies  which  are  wholly  insoluble  in 
this  menstrum;  they  are  also,  in  general,  difficultly 
soluble  in  alcohol.  They  generally  dissolve  in  ether, 
and  the  liquid  hydro-carbons.  Their  specific  gravity 
is  lesG  than  that  of  water. 

Heat  destroys  them;  acrolein  is  usually  formed 
associated  with  other  products. 

Since  oil  and  water  repel  each  other,  many  other 
substances  may  be  protected  from  moisture  by  simply 
coating  them  with  oil.  Shoe-leather  may  be  rendered 
water-proof  and  iron  protected  from  rusting  by  greas- 
ing.  Wood,  saturated  with  oil,  will  last  for'  a  long 
time  when  buried  in  moist  ground. 

Stearin  ok  Stearine,  (from  arkap,  suet)  Cj^HnoOe, 
IS  prepared  by  melting  suet  in  turpentine;  the  two 
other  proximate  principles  present,  are  precipitated, 


FATS   AND   OILS. 


175 


S. 


ted  throuarh- 
Some  are 
ain  oils  re- 
oil;  others 
py  oil,  and 
lis,  and  are 
•inters'  ink, 


'  are  among 
asoluble  in 
,  difficultly 
'e  in  ether, 
ific  gravity 

lly  formed 

nany  other 
by  simply 
e  rendered 
J  by  greas- 
for  a  long 

;  the  two 
ecipitated, 


while  the  stearine  remains  in  solution.  It  is  separated 
from  the  liquid  by  water,  and  purified  by  several  re- 
crystallizations  in  ether  ;  it  fuses  at  71",  and  solidities 
at  60°. 

Berthelot  has  reproduced  stearine  synthetically,  by 
heating  3  parts  of  stearic  acid  with  one  part  of  glyc- 
erine, in  a  sealed  tube. 

This  synthesis,  as  well  as  other  researches,  estab- 
lishes the  fact  that  the  neutral  fats  are  compound 
ethers  of  glyceryl,  and  the  fatty  acids. 

On  account  of  the  heat  generated  by  oxidizable 
oils  when  exposed  to  the  air,  frequent  instances  of 
spontaneous  combustion  occur  when  cotton  rags,  or 
waste  soaked  with  oil,  are  allowed  to  remain  in  a  heap. 

Fats,  especially  if  mixed  with  nitrogenous  matter, 
become  acid,  rancid.  The  chemical  nature  of  this 
change  is  not  entirely  understood. 

Olein  or  oleink,  is  the  chief  constituent  of  olive  oil 
and  fish  oil.  Berthelot  has  shown,  by  the  action  of 
oleic  acid  on  glycerine,  that  natural  oleine  is  a  mix- 
ture of  monoleiue,  dioleine,  and  trioleine.  Oleine 
heated  with  a  small  quantity  of  mercury  nitrate,  or 
any  other  body  capable  of  furnishing  nitric  oxide,  be- 
comes solid,  owing  to  the  transformation  of  the  oloi);3 
into  an  isomeric  body,  elaidlne.  Siccative  oils  contai.  ., 
instead  of  oleine,  another  principle  called  elaitie. 

Neutral  fatty  bodies  and  other  ethers  of  glycerine 
are  decomposed  by  alkaline  solutions ;  a  combination 
with  water  takes  place,  glycerine  and  fatty  j..:<'8  are 
formed.    We  may  take  as  an  example,  stearin. 


p 


176  ORGANIC    CHEMISTRY. 

3KHO+C5,TI„o06=2(KC,8H350,)+CaH803. 

AlkalieH,  therefore,  react  upon  the  ethers  of  glycerine 
in  the  same  manner  as  do  the  ethers  of  glycol  and 
ordinary  alcohol.  This  reaction  is  called  sapnmficor 
tion,  and  soaps  are  salts  formed  by  stearic,  margaric, 
and  oleic  acids,  with  a  metal. 

SOAPS.      BIEARINE  CANDLES. 

The  only  soluble  soaps  are  those  whose  base  is 
potassa  or  soda.  Soda  soaps,  those  ordinarily  in  use, 
are  hard,  while  potassa  soaps  are  soft.  On  adding  to 
an  aqueous  solution  of  soap  a  solution  of  a  metal,  a 
precipitate  is  formed  which  is  the  soap  of  the  metal 
emjiloyed  ;  thus  the  precipitate  which  common  water 
produces  in  soap  is  a  lime  soap. 

Ordinary  soap  is  made  by  boiling  fats  of  inferior 
quality -.vith  an  alkaline  solution.  When  the  oil  is 
completely  decomposed  the  soap  is  precipitated  by 
salt  watei',  in  which  soap  is  insoluble. 

Stoariiie  candles  have  hitherto  been  made  by  saponi- 
fying suet  or  tallow  with  lime  in  the  presence  of  boiling 
water.  At  present  the  amount  of  lime  employed  in 
the  saponification  is  considerably  diminished  (amount- 
ing to  only  4  per  cent.)  by  operating  at  a  temperature 
of  150-. 

The  saponification  of  fats  of  inferior  quality  is  also 
efff^cted  by  means  of  sulphuric  acid  instead  of  lime; 
this  acid  forms  with  the  fatty  acids,  double  or  conju- 


tmmK3-- 


FATS    AND    OILS. 


177 


'sHgOs. 

of  glycerine 
glycol  and 
saponificor 

c,  margaric, 


>8e  base  is 
irily  in  use, 
I  adding  to 
a  metal,  a 
'  tlie  metal 
imon  water 

of  inferior 

the  oil  is 

pitated  by 

by  saponi- 
I  of  boiling 
iployed  in 
i  (amount- 
mperatiire 

lity  is  also 
of  lime; 
or  conju- 


gate acids,  which  are  decomposed  by  water.  The  de- 
composition of  fats  into  their  constituents,  the  fatty 
acids  and  glycerine,  for  the  manufacture  of  candles,  is 
at  present  effected  on  a  large  scale  by  simply  heating 
the  fats  with  steam  under  pressure,  and  at  a  tempera- 
ture of  260°.  This  is  the  celebrated  process  of  the 
American  inventor,  Tilghman,  to  whom  the  wonder- 
ful "  sand  blast "  is  also  due. 

This  decomposition  of  fats  is  most  remarkable,  as, 
by  the  same  process,  only  at  a  lower  tempei'ature, 
Berthelot  obtained  a  result  exactly  the  reverse,  caus- 
ing stearic  acid  and  glycerine  to  reform  stearine  by 
simple  direct  synthesis. 

Steajuo  acid,  OigrijoOa.  is  crystalline,  insoluble  in 
water,  soluble  in  alcohol  and  ether,  and  melts  at  70°. 
It  unit-ss  with  the  bases ;  its  alkaline  salts  alone  are 
soluble. 

Mai{Gario  ob  Palmitio  acid,  C17H34O2,  (from 
fxapyafjov,  a  pearl,  owing  to  its  pearly  lustre)  is  crys- 
talline. It  melts  at  eO''  and  forms  salts  with  the  metals. 

Olkio  acid,  CigHsjOa,  is  an  oil  becoming  colored  in 
the  air  and  converted  into  an  acid  callec  elaidio  acid., 
which  is  fusible  at  44°,  in  contact  with  e  s.nall  qiiantity 
of  hyponitric  acid. 

These  three  a  'ids,  stearic,  margaric,  and  oleic,  are 
those  that,  with  glycerine,  constitute  most  of  the  natu- 
ral fats,  or  glyceryl  ethers, 

V  Lead  plasikr  is  essentially  a  lead-soap  compound 
of  plumbic  oleate. 


178 


OKGANIO    CHEMISTRY. 


OROTON  OIL. 

This  oil  is  extracted  from  the  seed  of  the  Croton 
tiglium  of  the  family  of  euphorbiacese. 

The  seeds  are  ground  and  expressed,  or  they  are 
treated  with  ether,  which  is  afterwards  driven  off  by 
distillation. 

This  oil  is  yellowish,  very  bitter,  and  possessee  a 
disagreeable  odor.  Alcohol  and  ether  dissolve  it.  It 
produces  blisters  whenever  it  comes  in  contact  with 
the  skin,  and  is  a  drastic  poison. 

Pelletier  and  Caventou  have  extracted  from  this  oil 
an  acid  body,  C4H602,  denominated  orotonio  acid. 

COD-LIVER  OIL. 

This  oil  is  extracted  from  the  liver  of  the  cod,  and 
several  other  species  of  the  genus  Gadus.  Two  pro- 
cesses are  employed  for  its  extraction  ;  either  tlie  oil 
is  obtained  by  putrefiactioii,  in  which  case  the  oil 
separates  out  naturally,  or  the  livers  are  cut  in«o  small 
pieces  and  heated  in  large  pans,  then  placed  in  cloth 
sacks  and  pressed.  It  is  of  a  brownish  color.  A  white 
oil  is  sometimes  sold,  which  has  been  bleached  by 
treatment  with  weak  lye  and  animal  charcoal.  The 
efficiency  of  this  latter  oil  is  much  less  than  that  of 
the  natural  oil. 

There  has  been  found  in  this  oil  3  to  4  tiionsandths 
of  iodine,  and  a  small  quantity  of  phosphorous  ;  and 
its  medical  qualities  are  thought  to  be  due  to  these 


P  the  Croton 

or  they  are 
riven  off  by 

possesses  a 
solve  it.  It 
:'ontact  with 

from  this  oil 
io  aoid. 


he  cod,  and 
Two  pro- 
ither  the  oil 
ase  the  oil 
t  in?-o  small 
ed  in  cloth 
•r.  A  white 
ileached  by 
pcoal.  The 
ban  that  of 

honsandtha 
irons ;  and 
le  to  these 


WAX. 


m 


two  snbstances,  but  it  is  probable  that  its  efficiency  is 
more  frequently  due  simply  to  its  fatty  character. 

BUTITSB. 

Ordinm-y  Butter.  Butter  contains  stearic,  mar- 
garic,  oleic,  and  butyric  acids,  and  several  other 
proximate  neutral  principles.  Its  density  is  0.82.  It 
dissolves  in  30  per  cent,  of  boiling  common  alcohol. 
The  odor  which  it  emits  on  becoming  rancid  is  due  to 
the  liberation  of  fatty  acids. 

"  Oleo-margarine''''  is  artificial  butter,  consisting 
mainly  of  oleine  and  margarine  obtained  from  suet  or 
lard. 

SPEBMACErn. 

This  substance  which  is  formed  in  peculiar  cavities 
in  the  head  of  the  6p3rm  whale,  and  is  a  neutral 
fatty  bofly  sometimes  employed  in  pharmacy.  It  is 
an  etiier,  which,  on  saponificntion,  produces  a  fatty  acid 
called  ethalio  acid,  and  a  monatoraic  alcohol,  ethal. 

HaO+C3,He40,=C,eTl3,OHO  +  Cell^O 


Spermaceti.         Bthaltc  Acid. 


WAX. 


KllMl. 


Yellow  bees-wax  is  obtained  by  Hi]l)mittiiig  honey- 
comb to  pressure,  then  fusing  the  sauie  luider  boiling 
water.  It  is  bleached  by  being  cut  into  tliin  cakes 
and  exposed  to  the  air  and  sunlight.     Thus  prepared 


180 


ORGANIC    CHEMISTRY 


ll       I- 


It  fuses  at  62°.     Mixed  with   3  per  cent,  of  oil  of 
sweet  almonds  it  forms  a  cemte,  used  in  pharmacy 

On  being  treated  with  alcohol  it  separates  into  two 
proximate  principles:  one,  soluble  in  this  liquid,  is 
acid  a^d  is  called  cerotio  ao«f,  having  the  formula 
C27H51O;  the  other,  which  is  but  slightly  soluble  is 
called  myricin.  The  latter  is  a  compound  ether, 
and  IS  decomposed  by  bases  into  an  acid,  ethaUo  acid, 
and  an  alcohol,  melisaie  alcohol,  CaoHc^O. 

CASTOR  OIL. 

This  Oil  is  extracted  from  the  Ricinm  vommmcU,  a 
plant  of  the  family  of  Euphorbiacese. 

The  castor-oil  beans  are  hulled,  pulverized,  and 
tlie  pasty  mass  obtained  Bubjected  to  strong  pressure. 
Ihis  oil  18  slightly  yellow.  Its  density  is  0.926  at 
12",  a:id  it  remains  liquid  at  a  temperature  of -IS » 
It  is  very  soluble  in  alcohol,  a  characteristic  which 
distinguishes  it  from  most  other  oils. 

This  oil  is  also  an  ether  of  glycerine;  the  acid  which 
It  contains  is  ricinoleic  acid,  G^^^O^. 


SUGARS. 


181 


It.  of  oil  of 
pharmacy, 
ates  into  two 
lis  liquid,  is 
the  formula 
7  soluble,  is 
)ounci  ether, 
ethalio  acid, 


'ommitms,  a 

t^erized,  and 
tig  pressure, 
is  0.926  at 
ire  of -1S<*. 
ristic  which 

acid  which 


SUGARS. 

The  general  name  of  stigars,  by  some  regarded  as 
polyatomic  alcohols,  is  given  to  bodies  which  are  capa- 
ble of  fermenting,  tliat  is,  of  decomposing  directly  or 
indirectly  into  different  products,  of  which  the  princi- 
pal ones  are  alcohol  and  carbon  dioxide.  Fermenta- 
tion requires  tlie  presence  of  certain  microscopic 
plants,  and,  according  to  Pasteur,  is  a  phenomenon 
correlative  witii  the  vital  development  of  these 
organisms.  This,  however,  has  been  latterly  dis- 
proved by  Tyndall. 

Sugars  may  be  divided  into  three  classes.  In  the 
first  are  those  in  which  the  proportion  of  hydrogen 
is  more  than  sufficient  to  convert  the  whole  of  the  oxy- 
gen  into  water.     It  contains  : 

Mannite,  CaH,,()fi,  extracted  from  manna. 

Duloite  or  melampyrite^  CelluOs,  found  in  Mada- 
gascar. 

Finite^  CglliaOs,  extracted  from  a  Calitbrnian  pine 
tree. 

Queroite,  CgHiaOs,  extracted  from  acorns. 

These  bodied  do  not  fei-ment  with  beer  yeast  alone; 
but  in  presence  of  certain  ferments  and  calcium  car- 
bonate they  furnish  alcohol,  carbon  dioxide,  and  hy- 
drogen. 

Sugars  of  the  second  and  third  class  contain  hydro- 
gen and  oxygL'n  in  the  proportions  to  form  water. 


182 


ORGANIC    CHEMISTRY. 


The  second  class  includes  the  glucoses,  iso-^.^eric 
bodies,  whose  general  formula  is,  C,H«0,.  Among 
the'3e  are: 

Ordinary  Ghicose  or  grwpe  mga/r. 

Zevulose,  as.socii.red  with  glucose  in  the  form  of 
inverted  sugar. 

Maltose,  obtained  fi-onj  malt. 

Galactose,  obtained  by  treating  sugar  of  milk  or 
gums,  with  dilute  adds.  ' 

IJucalin,  obtained  by  the  action  of  maltose  on  beer 
yeast. 

SorUn  exists  in  the  berries  of  the  mountain  ash. 
Inosite  is  foimd   in  the  embryo  of  young  plants 
and  in  the  fluids  of  flesh. 

Lactose  or  Sugar  of  MUk.    The  glucoses  may  be 
divided  into  two  series.   The  first  includes  those  bodies 
(ordinary  glucose,  levulose)  which,  on  being  oxydized, 
form  saccharic  acid,  and  on  being  hydrogen  ized  by 
means  of  Podium  amalgam,  produce  mannite.    The 
secora  includes  those  substances  (galactose,  lactose) 
wJr/ch,  on  oxydation  produce  mucic  acid,  and  on  hydro- 
^i-enation  furnish  dulcite.      The  third  class    of  su- 
gars contains  bodies  whose  general  formula  is  CijIIaOu, 
and  are  called  saccharoses,  by  Berthelot.     It  contains, 
besides  cane  sugar,  three  bodies  called: 

Melitose,  an  exudation  of  certain  eucalypti. 

TreMlose  or  mycose.,  extracted  from  the  Turkish 
manna  and  certain  mushrooms. 

Melezitose,  obtained  from  an  exudation  of  the  larch. 

The  sugars  r.f  the  first  two  classes  are  placed  by 
Berthelot  among  the  polyatomic  alcohols. 


MANI^^ITE. 


188 


68,    UOi'cOric 

Je-      Among 


the  form  of 

of  milk,  or 

iose  on  beer 

tain  ash. 
►ung  plants 

368  may  be 
hose  bodies 
»  oxjdized, 
genized  by 
nite.  The 
se,  lactose) 
d  on  hydro- 
1S8    of    8U- 

[t  contains. 


•ti. 

le  TurloBh 

'  the  larch, 
placed  by 


MANNITE. 

Cell^Oe. 
This  body  exists  naturally  in  an  exudation  of  vari- 
ous species  of  ash   {Fraximia  rotundlfolia),  called 
inanna,  of  which  it  forms  the  greater  portion.     It  is 
also  found  in  mushrooms,  algae,  the  sap  of  mopi   fruit 
trees,  onions,  asparagus,  celery,  etc.     It  nin       e  pre- 
pared by  dissolving  manna  in  one-half  it-  ^-t  ut 
water,  to  which  a  small  quantity  of  e^g  ]« 
added,  and  the  mixture  brought  to  boiling;,  m  ,  .oreu. 
On  cooling,  colored  crystals  are  deposited  which  are 
expressed  and  redissolved  in  hot  water.    This  solution 
is  mixed  with  animal  charcoal,  boiled  and  filtered  while 
hot.    The  liquid  deposits  crystals  on  cooling.    Man- 
nite  crystallizes  in  rhombic  prisms  and  has  a  sweet  taste. 
It  dissolves  in  seven  times  its  own  weight  of  cold  wa- 
ter, is  slightly  soluble  in  alcohol,  and  insoluble  in  ether. 
Its  solutions  are  optically  inactive. 

Mannite  fuses  at  about  165°;  at  about  200°  it  yields 
a  certain  quantity  of  a  substance  called  Mannitane, 
CjIIijOj.  It  oxydizes  in  presence  of  platinum  black, 
fiirnishing  a  non-crystallizable  acid  called  mannitio 
acid.  Boiling  nitric  acid  converts  it  into  saccharic 
and  oxalic  acids. 

Mannite,  treated  with  a  small  quantity  of  nitric  acid, 
is  changed  into  a  body  insoluble  in  water,  called 
mtro-mannite,  ^^"q  «)  1 0«,  which  may  be  regarded 
as  a  compound  ether. 

Buloite.—Dixlcite  is  very  analogous  to  mannite,  but 
differs  from  it,  in  that  it  furnishes,  with  nitric  acid, 
raucic  acid. 


a. 


T^^? 


184 


OKGAXIO    CUE.MISTBY. 


GLUCOSKS. 

CeII,,0«. 

Tliese  compounds  may  be  considered  as  representa- 
tive  carbohydrates.  Ordinary  glucose  (from  yXvnv?, 
sweet,)  or  grape  sugar,  isacrystalline  substance,  and  is 
found  in  honey,  tigs,  and  various  other  fruits,  together 
with  anotlier  insoluble  glucose.  It  has  been  found  in 
small  quantity  in  the  liver  and  in  most  of  the  fluids 
of  the  body.  It  is  obtained  by  the  decomposition  of 
sahcme,  tannin,  and  other  substances,  which,  for  this 
reason,  have  been  named  glucosldes. 

Vegetable  cellulose,  the  envelope  of  many  inverte- 
brates (chitin  and  tunicin)  and  the  glyeogenons  princi- 
l)le  of  the  liver  furnish  glucose  on  treatment  with 
dilute  acids. 

It  is  manufactur  ,.  on  .i  large  scale  by  the  action  of 
starch  upon  diluto  sulphuric  acid.  Water  containing 
four  to  eight  pi-  cent,  of  sulphuric  acid  is  placed  in 
vats  and  heated  to  boiling  by  means  of  superheated 
steam.  Before  the  water  boils,  starch  mixed  with 
water  is  added,  and  ebullition  maintained  as  long  as  a 
small  quantity  of  the  mixture  gives  a  blue  reaction 
with  iodine.  The  sulphuric  acid  is  not  changed  during 
this  transformation. 

It  is  then  saturated  with  ehalk  and  the  liquid  allowed 
to  become  clear.    It  is  decolored  by  passing  through 


3  representa- 
om  yXvHvs, 
:ance,  and  is 
its,  together 
en  found  in 
if  the  fluids 
nposition  of 
ch,  for  this 

■ny  inverte- 
iions  princi- 
raent  with 

le  action  of 
containing 
phiced  in 
nperheated 
lixed  with 
s  long  as  a 
e  reaction 
ged  during 

lid  allowed 
g  through 


I 


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5S«s**i!BS!^>S*^.-S*    " 


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IMAGE  EVALUATION 
TEST  TARGET  (MT-3) 


1.0 


l^|2^    12.5 

|5o  ■^~     M^H 

*^  1^    III  2.2 

""  !:::  !!!!!2.o 


1.1     l.'^H 


1.8 


Photographic 

Sciences 

Corporation 


1.25  1  1.4 

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6"     - 

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S' 


33  WEST  MAIN  STREET 

WEBSTER,  N.Y.  14580 

(716)  872-4503 


CIHM/iCMH 

Microfiche 

Series. 


CIHM/ICMH 
Collection  de 
microfiches. 


Canadian  Institute  for  Historical  MIcroreproductlons  /  Instltut  Canadian  de  microreproductions  historiques 


1 


GLUCOSES. 


185 


filters  containing  animal  charcoal  and  evapoi-ated  to  a 
density  of  4V  Bauine.  The  glucose  crystallizes  in 
compact  masses.  Often  the  liquid  is  evaporated  to 
only  3°  B.,  when  a  syriip  is  obtained  kno\vn  as  starch 
aijrup.  Honey  treated  with  cold  concentrated  alcohol, 
also  furnishes  glucose.  The  crystals  of  glucose  ai-e 
small,  opaque,  and  ill  defined. 

They  are  represented' by  the  formula  C«H,jOe,2H20, 
bnt  they  may  be  obtained  having  the  composition 
CeHiaOg  by  precipitating  the  glucose  in  boiling  concen- 
trated alcohol.  The  water  may  also  be  driven  off  by 
heating  the  glucose  to  about  100°. 

Glucose  is  soluble  in  a  little  more  than  its  own 
weight  of  water.     Weak  alcohol  dissolves  it  readily. 
It  is  slightly  soluble  in  cold  concentrated  alcohol. 
^  Its  solutions  turn  the  plane  of  polarization  to  the 
right.     This  rotatory  power  is  feeble  in  the  cold. 

Glucose,  heated  to  about  170°,  acts  in  the  same  man- 
ner as  mannite.  Gelis  has  demonstrated  that  it  loses 
a  molecule  of  water;  the  body  formed  CeHioOs,  is 
called  glucoaane,  CcMnO,=CMxo<\  +  B.^O.  It  re- 
produces glucose  on  being  boiled  with  acidulated 
water.  If  glucose  is  boiled  with  dilute  nitric  acid, 
saccharic  and  oxalic  acids  are  formed.  Fuming  nitric 
acid  forms  with  glucose  a  very  explosive  compound. 

Hydrochloric  acid  turns  it  brown.     With  dilute  sul- 
phuric acid  it  furnishes  a  double  acid  {auiphoylucio 
acid)',  with  strong  sulphuric  acid,   carbon.     Glucose 
oxydized  with  care,  fnrnishes  saccharic  acid. 
Heated  to  100°  with  butyric,  or  various  other  acids, 


186 


ORGANIC   CHEMISTRY. 


it  loses  water,  and  the  glucosane  formed  reacts  upon 
che  acid,  forming  an  ether,  saccharide,  or  dibutyrio 
glucosane, 

(0«H«) 

(C4H;0)Hj 


[0. 


Tliis  body,  as  well  as  other  saccharides,  are  decom- 
posed under  the  action  of  boiling  acidulated  water, 
into  an  acid  and  glucose. 

Glucose  combines,  with  sodium  chloride,  forming 
several  crystalline  compounds;  it  also  forms  unstable 
compounds  with  the  metallic  bases, 

CaC.H,oOe 
BaCeHiiOj,  etc. 

P^ligot  has  shown  that  the  solutions  of  these  glucos- 
ates  are  gradually  changed  into  salts  of  a  special  acid 
called  gliudc  acid,  whose  formula  is 

Ci2H,g09. 

Cnpric  acetate  boiled  with  glucose  is  reduced  to  the 
state  of  suboxide. 

This  action,  which  is  very  slow  with  salts  of  copper 
with  inorganic  acids,  becomes  rapid  and  complete  in 
presence  of  alkalic  ^r  adding  glucose  to  a  solution 
of  copper  Bulpha**^  -s  salt  is  not  precipitated  by 
potassa.  If,  however,  the  liquid  is  heated,  it  deposits 
cuprous  oxide.  (Trommer's  test.)  This  reaction  is 
more   delicate   with  copper  salts,    whose  acids  are 


reacts  upon 
or  dihutyrio 


,  are  decom- 
ilated  water, 

ide,  forming 
rms  unstable 


tliese  glucos- 
special  acid 


duced  to  the 

ts  of  copper 
complete  in 
to  a  solution 
cipitated  bj 
1,  it  deposits 
reaction  is 
le  acids  are 


GALACTOSE. 


187 


organic.  A  mixture  is  used  of  copper  sulphate, 
Rochelle  salt  and  soda  (Feliling),  or  a  solution  of 
copper  tartrate  in  potassa.    (Barreswil.) 

Prof.  W.  S.  Haines  has  ibiind  in  glycerine  a  very 
desirable  substitute  for  the  tartrate  in  Fehling's  test. 
The  proportions  employed  by  him  for  qualitative  ex- 
aminations are:  cupric  sulphate,  30  grains;  potassic 
hydrate,  li  drachms;  pure  glycerine,  2  fluid  drachms; 
distilled  water,  6  ounces. 

LEVTTLOeE,    CgH^Oj. 

This  name  is  given  to  a  variety  of  glucose,  which  is 
found  in  many  fruits.  It  may  be  obtained  by  boil- 
ing inulin  with  water,  or,  better,  it  can  be  prepared 
from  cane  sugar  by  the  action  of  dilute  acids.  It 
differs  from  the  other  sugars  in  that  its  rotary  power 
diminishes  on  heating. 

GALACTOSE, 

CgHjjOj. 

This  body  is  produced  by  boiling,  for  two  or  three 
hours,  sugar  of  milk  with  water  acidulated  with 
sulphuric  acid.  It  is  soluble  in  water  and  insoluble  in 
alcohol;  nitric  acid  transforms  it  into  mucio  acid. 

mOSIN,  INOSITE  OR  MUSCLE  8UGAB. 

C,H,A+2HjO. 
This  substance  is  found  in  many  animal  organs,  and 


188 


ORQANIO    CHEMISTRY. 


is  the  chief  constituent  of  the  liquid  which  impreg- 
nates the  muscles. 

It  may  be  prepared  by  first  extracting  the  creatin 
from  the  muscles,  then  separating  the  iiiosic  acid  with 
baryta.  To  the  liquid  is  then  added  a  quantity  of 
sulphuric  acid  sufficient  to  precipitate  the  whole  of  the 
baryta  and  the  liquid  treated  with  ether,  which  dis- 
solves the  foreign  substances. 

The  aqueous  solution  is  removed  and  alcohol  added 
to  it  until  a  precipitate  is  formed.  Crystals  of  potas- 
sium sulphate  first  separate  out,  then  beautii'ul  crystals 
of  inosite.  This  substance  h«s  a  sweet  taste.  At  a 
temperature  of  100°  it  loses  two  molecules  of  water. 
It  dissolves  in  one-sixth  of  its  weight  of  water  while  it 
is  insoluble  in  ether  and  strong  alcohol. 

Inosite  is  without  action  upon  polarized  light.  It 
is  not  converted  into  glucose  by  the  action  of  dilute 
acids,  and  does  not  reduce  copper  salts.  Mixed  with 
milk  and  chalk  it  undergoes  lactic  fermentation. 
(Page  122.) 


SACCHAROSES 


189 


lich  irapreg- 

the  creatin 
iic  acid  with 
quantity  of 
wliole  of  the 
,  which  dis- 

cohol  added 
ftls  of  potas- 
til'ul  crystals 
taste.  At  a 
es  of  water, 
ater  while  it 

a  light.  It 
on  of  dilute 
Mixed  with 
srmentation. 


SACCHAKOSES. 
Ordinary  Sugar, 

This  body  exists  in  a  large  number  of  plants, 
though  it  is  almost  exclusively  extracted  from  the 
sugar-cane  and  beet-root. 

Tlie  sngar-cane,  Arunde  saccharifera,  contains  17 
to  20  per  cent,  of  sugar.  To  extract,  the  juice  of  the 
cane  is  first  obtained  by  expressing.  This  juice  repre- 
sents 60  to  65  per  cent,  of  the  total  weight  of  the  cane, 
and  would  alter  rapidly  in  the  air  if  care  were  not 
taken  to  bring  it  rapidly  to  a  temperature  of  70°,  and 
adding  a  quantity  of  lime.  The  juice  soon  becomes 
covered  with  foam  and  deposits  difterent  albuminoid 
and  other  matters,  which  are  precipitated  by  the  lime. 
It  is  decanted  into  pans  and  rapidly  evaporated.  The 
sugar  crystallizes  out,  and  the  mother  liquor  is  evapo- 
rated as  long  as  it  furnishes  crystals.  The  thick  liquid 
which  remains  is  molasses.  The  sugar  thus  obtained 
is  brown  sugar,  and  is  subsequently  refined. 

The  beet-root  most  rich  in  sugar  is  that  of  Silesia. 
It  contains  about  10  per  cent,  of  sugar.  Sugar  crys- 
tallizes in  clinorhombic  prisms.  They  may  Be  readily 
obtained  by  slowly  evaporating  a  solution  of  sugar. 


190 


OROANIO   CHEMISTRY. 


The  crystals  of  ordinary  sugar  are  very  small,  as  the 
syrup  is  made  to  crystallize  quite  rapidly.  Cold  water 
dissolves  three  times  its  weight  of  sugar;  Lot  water 
dissolves  it  in  all  proportions,  forming  a  syrupy  liquid. 
It  is  not  dissolved  by  cold  alcohol  or  ether.  Dilute 
alcohol  dissolves  it  in  proportion  as  it  is  more  or  less 
aqueous.  Its  solutions  are  dextrogyrate.  Sugar  melts 
at  about  180°,  and  yields  a  liquid  which  soUdifies 
to  a  vitreous,  amorphous  mass,  called  barley  sugar, 
which  becomes  opaque  and  crystalline  after  some  time. 

If  sugar  is  heated  a  little  above  this  point,  it  is 
transformed  into  glucose  and  levulosane. 

CiaHiBOu=OeHiA +0«H,oO,. 

Levuloiane. 

At  about  190°  sugar  loses  water,  becomes  brown, 
and  finally  furnishes  a  substance  which  is  commonly 
known  as  caramel.     According  to  Gelis  three  pro- 
ducts of  dehydration  are  formed,  oaratmlam,  oara- 
melene  and  oarameline.    At  a  temperature  of  aSO" 
to  250°  sugar  is  decomposed  into  carbon  monoxide, 
carbon  dioxide,  carbohydrides  and  different  empyreu- 
matic  products.     Sugar  is  transformed  slowly  in  the 
cold,  and  rapidly  at  80",  in  contact  with  dilute  acids 
into  inverted  sugar,  which  is  thus  called  on  account 
of  its  inverted  action  upon  polarized  light.    On  pro- 
longed ebullition  the  solution  is  rendered  brown  and 
ulmic  products  are  formed.    Sugar  reacts  with  barvta 
water  and  lime  water,  forming  different  compounds 
called  merates  or  saccharates. 


SUQAR    OF    MILK. 


191 


imall,  as  the 
Cold  water 
;  liot  water 
I'Upj  liquid, 
er.  Dilute 
nore  or  less 
Sugar  melts 
li  solidifies 
rley  sugar, 
'  some  time, 
point,  it  is 


les  brown, 
commonly 
three  pro- 
'ane,  oara- 
re  of  230" 
monoxide, 
empyreu- 
rly  in  the 
lute  acids 
n  account 
On  pro- 
>rown  and 
ith  barvta 
ompounds 


Tlie  solutions  of  these  sucrates  are  decomposed  by 
carbon  dioxide  :  sugar  is  reformed.  Rousseau  makes 
use  of  this  fact  in  the  manufacture  of  sugar  on  a  very 
large  scale. 

Sugar  does  not  ferment  immediately  in  contact 
with  Tbeer  veast. 

to 

8UOAB  OF  HILK,    LACTIN  OB  LACTOSE. 

CisHaOii  +  H2O. 

It  is  obtained  from  milk,  by  precipitating  the  casein 
with  a  few  drops  of  dilute  sulphuric  acid,  filtering 
and  evaporating  the  liquid. 

Crystals  are  deposited,  which  are  purified  by  re- 
dissolving  and  treating  with  animal  charcoal. 

In  Switzerland  large  quantities  of  sn^^r  of  milk 
are  made  by  evaporating  the  wkey  which  remains 
after  the  separation  of  the  cheese. 

The  crystals  of  this  body  are  rhombic  prisms. 
This  sugar  is  insoluble  in  ether  and  alcohol,  and 
requires  2  parts  of  boiling  and  6  parts  of  cold  water 
for  its  solution. 

Its  solutions  are  dextrogyrate.  At  a  terri,..ratnre 
of  about  140°  it  loses  H2O,  and  becomes  browii  sn:  (60° 
to  180°. 

In  presence  of  sour  milk  and  chalk  it  undergoes 
lactic  fermentation. 

Sugar  has  been  found  in  a  sample  of  a  saccharine 
matter  extracted  from  the  sap  of  a  sapodilla  tree,  the 
tree  furnishing  caoutchouc. 


102 


ORGANIC     OIIEMISTRY 


Reichardt  has  obtained  (60-'75-807)  from  a  su^ar 
distinct  from  ordinary  sugar,  a  body  though  having 
the  same  formula.     He  names  it^am-amJm. 

HONEY. 

Honey  is  produced  by  the  domestic  bee  (Apis  mel- 
hfica),  an  insect  of  the  order  Hymenoptera. 

It  is  separated  from  the  wax  by  exposing  the  honey- 
comb to  tlie  sun,  on  wire  nets;  very  pure  lioney  is 
thus  obtained.  "^ 

Tlie  mass  which  remains  is  expressed,  andtliis  prod- 
uct 18  a  second  quality  of  honev,  more  colored  and 
of  a  less  agreeable  taste  and  odor  than  the  first  The 
comb  is  then  heated  with  water  to  remove  the  remain- 
derof  the  honey.  The  wax  thus  isolated  is  melted 
and  run  into  moulds.  Honey  owes  its  sweet  taste  to 
several  sugars.  There  is  found  in  it  a  dexti-oyrgate, 
crystalhzable  glucose,  and  on  removing  this  sugar 
there  remains  a  viscid  uncrystallizabJe  liquid,  which 
contains  levnlose.  In  addition  to  these,  small  quan- 
tities of  ordinary  sugar  have  also  been  found  in 
honey. 

GLUCOSIDES. 

This  name  is  given  to  certain  bodies  which  have 
the  property  of  forming  various  products  by  combin- 
mg  with  water,  amoi.g  which  is  glucose,  or  some  other 
sacchanne  matter. 

This  change  is  produced  by  the  action  of  acids, 
bases,  or  by  the  action  of  ferments.  We  cite  the  fol- 
lowing, but  shall  only  study  the  most  important: 


GLUC08IDK8. 


193 


'om  a  sugar 
ugh  Laving 
hin. 


I  (Apis  mel- 

;  the  honey- 
re  lioney  is 

1  tliis  prod- 
olored  and 
Srst.  The 
he  remain- 
is  melted 
eet  taste  to 
icti-oyrgate, 
this  sugar 
aid,  which 
mall  quan- 
found   in 


liich  have 
y  combin- 
ome  other 

of  acids, 
te  the  fol- 
tant: 


Salicin,  CisH.gO;,  extracted  from  the  bark  of  the 
Willow. 

Amygdalin,  CajH^NOn,  extracted  from  the  Bitter 
Almond,  Amygdahis  covimunis. 

Orcin,  O^IIsOo,  extracted  from  various  Lichens. 

Tiinnin,  G^HaOni  extracted  from  the  Oak. 

Phlorizin,  CaiHjjOio,  extracted  from  the  Apple,  Pear, 
or  Cherry  tree. 

Populin,  C20H22O8,  extracted  from  Aspen  leaves. 

Arbutin,  C13H16O7,  extracted  from  the  leaves  of  the 
Uva-Ursa. 

Convolvulin,  C31H50O16,  extracted  from  the  Convol- 
vulus orizahensia  and  mliiedeamis. 

Jalappin,  Q^^Q^^  exti-acted  from  Convolvulua 
orizahensu  and  scammoniu. 

Saponin,  a  white  amorphous  powder  whose  solution 
is  very  frothy  and  of  which  the  powder  is  very  sternu- 
tatory, 

Daphnin,  CsiHsaOn,  the  crystalline  matter  extracted 
from  the  bark  of  the  Ash  {Fmxinus  excelsior). 

Cyclamin  CaoH240,o,  extracted  from  the  tubercles  of 
the  Cyclamen  europceum. 

Quinovin,  CaotligOg,  a  resinous,  bitter  matter,  solu- 
ble in  alcohol,  existing  in  the  bark  of  the  Quina  nova 
and  other  cinchonas. 

Solanin,  C43H71NO16.  This  has  already  been  studied, 
(page  165). 

Esculin,  C21H.24O13,  extracted  from  the  bark  of  the 
Horse  Chestnut. 

Qnercitrin,  CjgHaoOn,  from  the  bark  of  the  yellow 
oak  {Quercus  tinctoria). 


194 


ORGANIC   CHKMISTBy. 


Coniferin,  C.HaOs,  from  the  Larix  europaea,  etc. 
Vanillin,  from  the  Vanilla  bean,  and  recently  ob- 
tained artificially  (60-74-608). 

SA  Licra,  Call  igOi  +  IlaO. 

This  body  crystallizes  in  white  needles,  fusible  at 
120°,  insoluble  in  ether,  soluble  in  alcohol  and  water. 
These  solutions  are  levogyrate  and  very  bitter.  It  is 
used  as  a  febiifuge,  but  is  of  little  value  in  well  de- 
fined intermittent  fevers. 

Tt  has  as  a  distinguishing  chemical  character,  the 
pioperty  of  becoming  red  with  sulphuric  acid. 

Under  the  action  of  dilute  sulphuric,  or  hydro, 
chloric  acid,  or  even  with  emulsin,  salicin  is  decom- 
posed.    With  the  latter  the  reaction  is: 

C.sH.807 + H,0=C«H,  A  +  C^HsOa 

Glucoge.       Saligenln. 

In  contact  with  cold  nitric  acid  it  loses  hydrogen, 
and  a  body  is  formed  called  helicin,  Ci^YL^^O-,. 

When  treated  with  oxydizing  agents,  it  gives  off  an 
odor  which  is  identical  with  that  of  the  essence  of 
meadow  sweet  {Spirea  vlmaria). 

This  body  is  produced  especially  when  salicin  is 
treated  with  a  mixture  of  sulphuric  acid  and  potas- 
sium bichromate,  and  is  also  known  by  the  name  of 
hydride  ofsalicyl. 

Its  formula  is  identical  with  that  of  benzoic  acid, 
C7H16O2,  but  it  has  not  the  properties  of  this  acid. 


8ALICIN. 


10ft 


ropaea,  etc 
recently  ob- 


s,  fusible  at 

I  and  water. 

i)itter.     It  is 

in  well  de- 

ici-acter,  the 

icid. 

,  or  hjdrou 

I  is  decom- 


\ 

-I 

J  hydrogen, 

jives  off  an 
essence  of 


1  salicin  is 
and  potas- 
le  name  of 

rizoic  acid, 
I  this  acid. 


It  is  an  aromatic  liquid,  boiling  at  196°,  and  has  the 
property  of  oxydizing  spontaneously,  giving  rise  to 
an  acid  called  salicylic  acid,  C7H4O3. 

Salicin,  treated  with  fused  potassa,  furnishes  potas- 
sium oxalate  and  salicylate.  Cahours  has  shown  that 
essence  of  Gaultheria  p'rocumhem,  a  heath  of  New 
Jersey,  contains,  besides,  an  isomer  of  the  essence 
of  turpentine,  a  sweet-scented  liquid,  boiling  at  220°, 
which  is  salicylic  methyl  ether,  and  is  re-converted, 
in  contact  with  alkalies,  into  methyl  alcohol  and  sali- 
cylic acid  :  it  may  be  produced  artificially  by  treating 
wood  ppirit  with  a  mixture  of  salicylic  and  sulphuric 
acids. 

Salicylic  or  oxyhemoio  acid  has  been  lately  pro- 
duced by  Kolbe  (56  -'74  -22),  by  a  remarkable  syn- 
thesis  in  acting  on  carbolate  of  sodium  with  COj. 

2C,H50m + C02=CeTI«0  -i-  0,H403Na,. 


Sodium  phenol. 


Sodium  salicylate  of  sodium. 


It  has  now  come  to  be  a  very  important  article  in 
pharmacy  and  in  the  arts,  on  account  of  its  efficiency 
as  an  antiseptic,  equaling  or  surpassing  carbolic  acid 
(phenol),  yet  without  the  unpleasant  odor  of  the  latter 
body,  or  its  toxical  qualities.  As  of  considerable  im- 
portance theoretically,  it  should  be  stated  that  Herr- 
mann has  very  lately  (60-April,  "TT)  obtained  salicylic 
acid  by  the  action  of  sodium  upon  succinic  ether. 


196 


ORGANIC   CHEMISTRY. 


TANNIXS. 

This  is  the  name  given  to  different  principles  exist- 
ing in  plants,  which  are  characterized  by  the  following 
properties: 

Ist.  They  give,  with  ferric  salts,  a  black  coloration 
approaching  bine  or  green. 

2d.  They  precipitate  solutions  of  albuminoid  sub- 
stances, particularly  those  of  gelatine. 

The  principal  ones  are: 

Tannin  of  oak,  C^HiaOn. 

"        "  cachou  (catechin  or  catechic  acid). 
"         "  quinqninia  (quinotannic  acid). 
"         "  coffee  (caffetannic  acid). 
"         "  fustic  (morintannic  acid). 

Oak  tannin  is  best  prepared  from  gall-nuts  which 
contain  much  more  than  does  the  bark.  The  nuts 
&ve  pulverized  and  submitted  to  the  action  of  commei-- 
cial  sulphuric  ether,  which  is  made  aqueous.  This 
€ther  may  be  replaced  with  advantage  by  a  mixture  of 
600  grams  of  pure  ether,  30  grams  of  90  per  cent, 
alcohol,  and  10  grams  of  distilled  water  for  every 
100  grams  of  gall-nuts.  After  twenty-four  hours  the 
apparatus  contains  two  layers  of  liquid;  the  upper  one 
is  ether,  containing  but  little  tannin,  while  the  lower 
one  is  a  very  strong  aqueous  solution  of  tannin. 

The  lower  layer  is  removed  md  evaporated  in  an 


inciples  exist- 
the  following 

ack  coloration 

•nmiiioid  sub* 


ic  acid), 
cid). 


ll-nuts  which 
£.  Tlie  nuts 
a  of  commer- 
ueous.  This 
a  mixture  of 
90  per  cent. 
3r  for  every 
ur  hours  the 
he  upper  one 
ile  the  lower 
mnin. 
orated  in  an 


TANNIN 


197 


oven  on  shallow  plates.  There  remains  an  amorphous 
spongy  substance,  very  soluble  in  water,  less  soluble 
in  alcohol,  and  almost  insoluble  in  ether.  Tliis  residue 
is  very  astringent  and  slightly  acid. 

Solutions  of  tannin  give  a  white  precipitate  with 
tartar  emetic. 

It  precipitates  solutions  of  the  alkaloids,  and  coagu- 
lates blood. 

With  solutions  of  gelatin  it  gives  a  voluminous  pre- 
cipitate, soluble  on  heating  in  an  excess  of  gelatin. 

Tannin  forms,  with  fresh  hide,  an  imputrescible  com- 
pound, which  is  leather.  The  art  of  tanning  is  based 
on  the  action  of  oak-bark  tannin  on  hides  from  which 
the  hair  has  been  removed,  usually  by  lime. 

Gallic  acid.  In  solution,  tannin  is  gradually  de- 
composed, the  liquid  becoming  covered  with  mould. 

Carbon  dioxide  is  disengaged  and  an  acid,  called 
gallic  acid,  is  formed. 

This  transformation  does  not  take  place  if  all  air  is 
excluded;  and  the  air  alone  is  not  sufficient.  It  requires 
the  presence  of  a  mycelium  of  a  mucedin  conveyed  to 
the  liquid  either  by  the  air  or  in  some  other  manner. 

This  transformation  is,  like  alcoholic  fermentation, 
a  phenomenon  correlative  with  the  development  and 
growth  of  an  organism.  On  boiling  tannin  with  water 
acidulated  witlx  hydrechloric  or  sulphuric  acid,  it  is 
decomposed  into  glucose  and  gallic  acid: 

C^,H«0„H-4HaO=3(C,H605)+C,H,A. 


Gallic  acid. 


Glucose. 


198 


ORGANIC    CHEMISTRY. 


GalUc  acid  is  deposited  as  the  liquid  becomes  cool 
It  18  purified  by  redissolvingand  treating  with  animal 
charcoal,  and  recrjstallizing. 

Gallic  acid,  C,R,0,=^^§^  |  o„  crystallizes  in  silky 
needles,  soluble  in  three  parts  of  boiling  water,  but 
little  soluble  in  cold  water.  This  solution,  on  standing 
m  the  air,  becomes  altered  after  a  long  time,  carbon 
dioxide  is  disengaged  and  the  solution  turns  brown- 
alkalies  accelerate  this  change.  ' 

Gallic  acid  produces  a  blue  color  with  ferric  salts 
and  precipitates  tartar  emetic,  but  does  not  precipitat^ 
gelatin  when  pure,  nor  the  alkaloids. 

Mixed  with  pumice-stone  and  heated  to  210°  it  pro- 
duces  a  beautiful  sublimate  otpyrogaUio  acid,  carbon 
dioxide  being  liberated  at  the  same  time. 

C7HgO5=0AO8+C02. 

This  body  occurs  in  colorless,  acicular  crystals, 
fusible  at  about  115»,  and  soluble  in  2.5  parts  of 
water.  Its  solution  absorbs  oxygen  from  the  air,  in 
presence  of  alkalies,  and  becomes  quite  brown. 

It  reduces  gold  and  silver  salts,  and  forms  unstable 
compounds  with  certain  acids.  It  may  properly  be 
placed  among  the  phenols.  This  body  is  employed 
in  photography,  and  in  the  laboratory.  Mercadante 
(47-'r4-484)  finds  that  gallic  acid  is  injurious  to 
vegetation,  inasmuch  as  it  combines  with  the  mineral 
food  of  the  plant  rendering  it  insoluble. 

Grimaux  was  the  first  to  consider  gallic  ftcid  aa 
tetratomic  and  monobasic  (77-620). 


VEGETABLE   CHEMISTRY. 


199 


Bcomes  cool, 
with  animal 

llizes  in  silky 

water,  but 
on  standing 
me,  carbon 
irns  brown; 

ferric  salts, 
;  precipitate 

210°  it  pro- 
loid,  carbon 


ir   crystals, 
.5  parts  of 

the  air,  in 
wn. 

IS  unstable 
roperly  be 

employed 
lercadante 
jnrions  to 
le  mineral 

io  acid  as 


VEGETABLE  CHEMISTRY. 

At  the  moment  when  the  radicle  of  a  plant  appears 
above  the  ground,  its  vital  phenomena  imdergo  a 
marked  change. 

The  plant  decomposes  carbon  dioxide,  water  and 
certain  nitrogenous  compounds  furnished  by  the  soil, 
and  grows  by  retaining  carbon,  hydrogen,  uitrogen  and 
a  little  oxygen,  and  returns  to  the  air  the  greater  part 
of  the  oxygen  derived  from  the  carbon  dioxide,  water 
and  nitrogenous  compounds. 

Bonnet  observed,  in  the  last  century,  that  leaves, 
exposed  to  the  snn  in  areated  water,  disengage  a  gas, 
which  Priestly  showed  is  oxygen.  Sennebier  discovered 
that  this  oxygen  is  derived  from  carbon  dioxide.  De 
Saussure  verified  these  facts,  and  demonstrated  that 
this  decomposition  of  carbon  dioxide  does  not  take 
place  in  the  dark,  and  t>.at  the  green  portions  of  the 
plant  alone  are  capable  of  effecting  the  change. 

J.  Belluci  (9-78-362)  has  lately  shown  that,  con- 
trary  to  former  belief,  none  of  the  oxygen  exhaled  by 
plants  is  in  the  form  of  ozone. 

ExPEBiKENT.— Place  a  few  leaves  in  a  flask  half  full 
of  water  containing  carbon  dioxide,  "soda  water,"  invert 
the  flask  over  a  glass  of  water,  and  expose  it  to  the  sun- 
light, after  having  covered  it,  if  the  sun  is  very  hot, 
with  a  sheet  of  transparent  paper;  minute  bubbles  will 


200 


ORGANIC    CHEMISTRY. 


soon  be  seen  to  form  on  the  leaves,  as  small  as  the  point 
of  a  pin,  will  increase  in  size,  unite  and  mount  to  the 
upper  part  of  the  flask.  Transfer  this  gas  to  a  test- 
tube,  and,  on  examination,  it  will  be  found  to  be  oxy- 
gen. Substitute  for  this  flask  an  opaque  vessel,  or  per- 
form the  experiment  in  the  dark,  and  the  cprbon  diox- 
ide will  not  be  altered  in  the  least. 

Wliere  do  the  plants  find  this  carbon  dioxide  ? 
Chiefly  in  the  air.  Boussingault,  in  order  to  demon- 
strate this,  placed  under  a  bell-glass  some  peas  planted 
in  calcined  sand;  he  watered  them  with  pure  distilled 
water,  and  passed  air  into  the  glass;  the  peas  grew, 
flowered  and  bore  fruit. 

ISTow  the  substance  of  these  peas  contained  carbon 
hydrogen  and  nitrogen,  in  much  greater  quantity 
than  the  seed  from  which  they  grew,  consequently 
these  constituents  were  taken  from  the  air  and  water. 
'  If,  however,  the  air  be  made  to  pass  through  an 
alkaline  solution  before  escaping  Irora  tlie  vessel,  no 
carbon  dioxide  is  absorbed,  which  also  proves  that  the 
carbon  dioxide  existing  in  the  air  has  been  removed 
by  the  plant.  Tlie  plant  takes  up,  in  the  same  man- 
ner, carbon  dioxide  from  the  water  which  passes  from 
the  soil  into  its  roots. 

Plants  are  also  capable  of  decomposing  water,  in 
fact,  Collin  and  W.  Edwardd  have  proved  that  tlie  sub- 
merged stems  of  the  Polygonum  tinctorium  and  cer- 
tain mushrooms,  exhale  hydrogen. 

On  the  other  hand,  Payen  has  proved  that  the  hy-  * 
drogen  exceeds  the  oxygen  in  the  woody  parts  of 


JL 


1 


VEGETABLE    CHEMISTRY. 


2U1 


I  as  the  point 
lount  to  the 
as  to  a  test- 
i  to  be  oxy- 
essel,  or  per- 
oprboii  diox- 

►n  dioxide  ? 
r  to  (lemon- 
peas  planted 
lire  distilled 
!  peas  grew, 

ined  carbon 
er  quantity 
onsequently 
and  water, 
through  an 
B  vessel,  no 
i^es  that  the 
3n  removed 
same  man- 
passes  from 

y  water,  in 
lat  the  sub- 
m  and  cer- 

• 

!mt  the  hy- 
ly  parts  of 


plants,  and,  indeed,  many  substances  produced  by 
plants,  as  oils  and  resins,  are  very  rich  in  hydrogen. 
In  short,  the  oxygen  contained  in  the  plant  would*not 
be  sufficient  to  oxydize  or  transform  into  water  the 
whole  of  the  hydrogen  it  contains,  consequently  it 
must  be  admitted  that  water  is  decomposed  by  plants. 
The  conditions  under  which  this  change  takes  place 
have  not  as  yet  been  determined. 

The  experiment  of  Boussingault  proves,  as  Ingen- 
housz  has  claimed,  that  the  air  furnishes  the  plant  with 
nitrogen;  but  where  does  this  nitrogen  come  from?  Is 
it  taken  by  the  plant  from  the  free  nitrogen  of  the  atmos- 
phere?  or  is  it  derived  from  the  nitric  or  nitrous  acids, 
or  from  the  ammonia  contained  in  the  atmosphere,  or, 
in  one  word,  from  the  nitrogenous  compounds  existing 
in  the  air?  ^ 

Boussingault  has  shown  that  while  certain  families 
of  plants,  principally  the  common  vegetables,  derive 
from  the  air  a  large  quantity  of  nitrogen,  even  taking 
up  free  nitrogen,  others,  the  cereals  for  instance,  derive 
nitrogen  chiefly  from  the  soil;  for,  on  causing  clover 
and  wheat  to  grow  in  calcined  sand  in  presence  of  air 
deprived  of  its  nitrogenous  compounds,  and  distilled 
water,  he  observed  that  the  clover  took  up  carbon,  hy- 
drogen,  water  and  nitrogen,  while  it  appears  that  the 
wheat  obtained  from  the  air  carbon  and  water  only. 

Nitrogen,  which  is  present  in  the  air  in  the  form  of 
ammonium  nitrate,  is  absorbed  by  all  plants.  Direct 
experiments  have  shown  that  the  salts  of  ammonium, 
especially  ammonium  nitrate,  constitute  an  ejicellent 


202 


ORGANIC    CHEMISTRY. 


compost,  and  consequently  this  nitrate  can  lose  its  oxy- 
gen, or  become  reduced  in  the  plant. 

Now,  it  is  known  that  urea  and  animal  excreta  are 
transformed  into  ammoniacal  compounds  on  exposure 
to  the  air;  therefore,  in  order  to  obtain  a  good  crop, 
even  with  plants  which  take  up  the  nitrogen  of  the  air, 
it  is  necessary  to  employ  manures  which  furnish  not 
only  easily  assimilated  nitrogen,  but  those  which,  be- 
sides, furnish  the  plant  with  soluble  organic  com- 
pounds and  the  mineral  substances  necessary  for  its 
development  and  growth.  Of  these  latter  there  is  re- 
quired for  the  plant,  potassium  and  calcium  chlorides, 
sulphates,  phosphates,  etc. 

With  the  four  elements,  carbon,  hydrogen,  nitrogen, 
and  oxygen,  natrre  forms  an  infinite  variety  of  com- 
pounds by  mysterious  methods,  to  which  we  have  not, 
as  yet,  the  key,  but  of  which  synthetical  research  gives 
us  some  idea.  Thus,  with  carbon  dioxide  and  water, 
Berthelot  produces  formic  acid;  with  formic  acid  he 
obtains  alcohol,  and  subsequently  acetic  acid.  Pasteur 
also  has  shown  that  glycerine,  one  of  the  principles  of 
fat,  is  produced  in  the  process  of  fermentation  and 
that  a  complex  acid,  succinic  acid,  is  also  fonned  under 
the  same  circumstances.  However,  we  are  far  from 
knowing  how  to  produce  those  substances  which  nature 
forms  at  ordinary  temperatures,  and  with  only  four 
elements.  What  wondrous  chemistry  is  that  of  the 
plant,  fitted  by  an  all-wise  Creator  to  elaborate  with 
such  simple  materials,  the  beauteous  violet,  the  fragrant 
rose,  or  the  luscious  fruit  1 


lose  its  oxy- 

excreta  are 
►n  exposure 
good  crop, 
1  of  the  air, 
furnish  not 
which,  be- 
came com- 
sary  for  its 
there  is  re- 
1  chlorides, 

1,  nitrogen, 
5ty  of  com- 
e  have  not, 
earch  gives 
and  water, 
lie  acid  he 
i.  Pasteur 
rinciples  of 
itation  and 
med  under 
e  far  from 
lich  nature 
only  four 
hat  of  the 
)orate  with 
be  fragrant 


VEGETABLE   CHEMISTRY 


203 


By  combining  six  atoms  of  carbon  with  five  atoms 
of  water,  nature  forms  either  the  woody  principle,  cd- 
luloae,  or  the  essential  constituent  of  the  potato,  8taroh. 
J3y  uniting  ten  atoms  of  carbon  with  sixteen  atoms  of 
hydrogen,  she  produces,  in  the  orange  and  in  the  pine, 
two  essences  or  oils  very  different  in  character.  By 
associating  the  four  organic  elements  she  forms  the 
most  different  substances,  the  nourishing  cere  ,1  as  well 
as  the  most  deadly  strychnia;  and  often  products  as 
nnhke  as  these  are  found  side  by  side  in  the  same 
plant. 

Thus  the  plant  is  a  structure  which  decomposes  car- 
bon  dioxide,  water,  and  compounds  of  nitrogen;  which 
forms  its  substance  out  of  carbon,  hydrogen,  nitrogen, 
and  a  part  of  the  oxygen  of  these  compounds,  and 
which  exhales  oxygen.  Hence,  chemically,  it  would  be 
proper  to  call  the  plant  a  reducing  apparatus. 

We  should  add  that  the  flowers  and  portions  of ' 
plants  not  green,  also  the  buds  in  developing,  produce 
an  exhalation  of  carbon  dioxide,  and  that  during  ger- 
mination, and  especially  during  the  time  of  flowering 
a  sensible  amount  of  heat  is  disengaged.  As  a  result 
ot  this  elevation  of  temperature,  there  is  produced  in 
plants  some  slight  oxydation  or  combustion,  as  in  the 
respiration  of  animals. 

Hence,  we  must  conclude  that  plants  and  animals, 
m  many  circumstances  at  least,  deport  themselves  in 
a  similar  manner. 

Many  experimenters,  and  especially  Dutrochet  and 
(iarreau,  go  further,  and  say  that  plants  aiid  animals 


204 


ORGANIC    CHEMISTRY 


respire  in  an  identical  manner,  and  according  to  their 
theories  all  living  creatures  take  up  oxygen  and  exhale 
carbon  dioxide. 

The  experiments  of  Garreau  especially  deserve  at- 
tention. He  placed  branches,  detached  or  affixed  to 
the  plant,  in  vessels  full  of  air,  and  exposed  them  to  a 
diffiised  light.  The  volume  of  the  air  was  known  and 
the  oxygen  absorbed  was  determined  by  a  special  con- 
trivance ;  the  carbon  dioxide  produced  was  removed 
by  placing  in  the  vessel  an  alkaline  solution  of  known 
weight.  Thus  the  variations  of  these  gases  were  care- 
fully studied. 

As  a  result  of  his  experiments  Garreau  claimed  to 
have  established  that  both  in  the  dark  and  in  the 
light,  there  is  an  absorption  of  oxygen  and  an  ex- 
halation of  carbon  dioxide,  but  the  amoimt  of  car- 
bon dioxide  collected  does  not  represent  the  amount 
really  exhaled,  as  the  greater  part  is  reduced  at  the 
moment  of  liberation.  From  these  facts  it  would 
appear  that  in  all  living  creatures  the  same  phenome- 
non of  respiration  takes  place,  which  consists  in  a 
consumption  of  oxygen  and  an  exhalation  of  carbon 
dioxide. 

This  phenomenon  is  associated  with  another  ;  viz., 
assimilation  or  nutrition.  It  is  here  that  the  differ- 
ence, indeed  a  complete  opposition,  between  the  two 
kingdoms  is  established.  The  plant  grows  by  re- 
ducing, under  the  influence  of  heat  and  sunlight, 
carbon  dioxide,  water  and  nitric  acid,  by  accumulating 
carbon,  hydrogen,  nitrogeu  and  by  exhaling  the  greater 


OBGAKIZED   SFBSTANOES. 


205 


ling  to  their 
a  and  exhale 

deserve  at- 
:>r  affixed  to 
sd  them  to  a 
I  known  and 
special  con- 
gas removed 
m  of  known 
8  were  care- 
claimed  to 
and  in  the 
and  an  ex- 
imt  of  car- 
tho  amount 
uced  at  the 
B  it  would 
le  phenome- 
jnsists  in  a 
1  of  carbon 

3ther  ;  viz., 
;  the  differ- 
(en  the  two 
ow8  by  re- 
d  sunlight, 
cumulating 
the  greater 


part  of  the  oxygen.  The  animal,  on  the  other  hand, 
forma  its  substance  from  that  of  the  plant,  oxydizing, 
or  consuming,  the  vegetable  products  with  the  oxy- 
gen of  the  air  exhaled  by  the  plants;  it  reduces  the 
complex  products  formed  in  the  vegetable  to  the  state 
of  carbon  dioxide,  water  and  ammonia;  thus  the  ani- 
mals supply  the  plants  with  food,  receiving  in  turn 
nourishment  from  them.  Those  desirous  of  further 
studying  this  and  other  interesting  topics  relating  to 
Vegetable  Chemistry,  will  find  very  valuable  the 
woi-ks  of  Prof.  S.  W.  Johnson,  "  How  Crops  Grow," 
and  "How  Oops  Feed";  also  Prof  John  C.  Draper's 
article  in  Am.  Jour.  Sci.  and  Arts,  Nov.  1872,  entitled 
"Growth  of  Seedling  Plants." 

ORGANIZED   StTBSTANCES. 

Among  the  chemical  substances  of  which  we  have 
spoken  certain  ones  participate  more  in  vital  phe- 
nomena, and  have  more  definite  physical  structure  than 
do  others. 

These  are  designated  as  organized  or  organisable 
mibstanoes,  the  term  organio  being  reserved  for  the 
definite  compounds  studied  in  organic  chemistry.  All 
these  substances  play  an  important  part  in  tiie  veget- 
able kingdom,  forming  the  network  of  vegetable  tis- 
sue, as  cellulose  or  as  starch,  etc. 

CELHTLOSE  OB  OELLTJLIN,   (CeHioOg)n. 

On  examining  a  young  plant  under  the  microscope, 


206 


OBGAino   CHEMISTRY. 


we  observe  that  it  is  built  up  of  little  cells  and  mi- 
nute,  diaphanous  ducts  or  vessels  filled  with  sap  and 
air.  The  material  of  which  these  tissues  are  com- 
posed is  called  cellulose.  The  pith  of  the  elder,  cot- 
ton fibre,  and  paper  are  almost  exclusively  composed 
of  this  substance. 

Cellulose  is  a  carbo-hydrate;  C.HioO,,  in  the 
formula,  ordinarily  given  to  it,  although  a  multiple 
formula  at  least  three  times  as  large,  or  CigHaoO,,  is 
necessary  to  explain  certain  reactions  with  nitric  acid. 
ExPEEiMEirr.  Pure  cellulose  may  be  obtained  in  the 
following  manner:  cotton,  linen  or  paper  is  treated  with 
dilute  alkaline  solutions,  washed  and  immersed  in  weak 
chlorine  water;  finally  it  is  submitted  to  the  action  of 
various  solvents,  as  water,  alcohol,  ether  and  acetic 
acid  until  nothing  more  is  dissolved. 

This  substance  is  solid,  white  and  insoluble.  It  is 
destroyed  at  a  red  heat,  producing  carbon  and  uumer- 
ous  carbohydrides,  gaseous  and  Hquid,  which  distil 
over.  With  monohydrated  sulphuric  acid  it  produces 
a  colorless,  viscid  liquid,  which  contains,  at  first,  an 
insoluble  substance  having  the  properties  of  starch  and 
yielding  a  blue  color  with  iodine.  If  the  action  of  tlie 
acid  is  continued,  the  whole  is  dissolved  and  the  sai^e 
products  are  obtained  as  in  the  case  of  starch  when 
brought  in  contact  with  srilphuric  acid,  i.  e.  dextrin 
and  glucose.  To  separate  the  latter  substance,  it  is 
simply  necessary  to  saturate  the  acid  with  chalk  and 
evaporate  the  liquid. 
Concentrated  hydrochloric  acid  produces  the  same 


CELLULOSE. 


207 


Us  and  mi- 
;h  sap  and 
8  are  coin- 
elder,  cot- 
^  composed 

1O5,  ia  the 
I  multiple 
^isHaoOjj  is 
nitric  acid, 
ned  in  the 
eated  with 
ed  in  weak 
>  action  of 
and  acetic 

ble.  It  is 
id  uumer- 
lich  distil 
t  produces 
it  first,  an 
starch  and 
ion  of  tlie 
the  sante 
ireh  when 
B.  dextrin 
ince,  it  is 
;halk  and 

the  same 


^ect.  If  paper  be  immersed  for  an  instant  only  in 
sulphuric  acid,  diluted  with  half  its  volume  of  water, 
and  carefully  washed,  it  acquires  the  toughness  of 
pai-chment.  Paper  thuo  prepared  is  fipequently 
employed  in  experiments  on  dialysis;  it  is  also  much 
used  by  pharmacists  to  cover  the  stoppers  of  bottles. 
It  is  known  in  commerce  as  vegetable  parchment. 

OUN  COTTON  OR  PYEOXTLIN. 

Gun  cotton  was  first  made  by  Schoenbein,  in  1846. 

To  prepare  it  cotton  is  plunged  for  two  or  three 
minutes  into  fuming  nitric  acid,  or,  better,  into  a  mix- 
ture of  1  vol.  nitric  acid  (of  a  density  of  1.6),  and  2 
vols,  of  strong  sulphuric  acid;  it  is  then  thoroughly 
washed  and  dried  at  a  low  temperature. 

The  cotton  is  not  changed  in  appearance  other  than 
becoming  «omewhat  wrinkled.  When  well  prepared 
it  bums  completely,  leaving  no  residue.  The  tem- 
perature at  which  it  takes  fire  varies  from  100"  to  180° 
according  to  the  manner  in  which  it  has  been  pre- 
pared. It  is  cellulose  in  which  from  six  to  nine  atoms 
hydrogen  have  been  replaced  by  an  equivalent  quan- 
tity of  the  monad  radicle  NOa  that,  having  the 
formula  CigHaOuONOj,  has  the  greatest  explosive 
energy.  Pyroxylin  regenerates  cellulose  in  contact 
with  ferrous  chloride.  K  cellulose  be  considered  a  sort 
of  alcohol,  as  claimed  by  some,  pyroxylin  would  be  a 
nitric  ether  of  this  alcohol. 

Pyroxylin  has  the  advantage  over  gunpowder  of 


208 


ORGANIC   CHEMISTRY. 


bem^  more  easily  prepared,  and  of  remaining  unaf- 
fected by  moisture,  but  its  cost  is  relatively  greater, 
and  Its  shattering  power  renders  its  employment 
dangerous. 

The  term  collodion  (from  «oAA«,  glue)  is  given  to  a 
preparation  obtained  by  dissolved  gun-cotton  in  a 
mixture  of  1  part  of  alcohol  and  4  parts  of  ether, 

Chas.  H.  Mitchell  has  made  (62-74-236)  a  number 
of  experiments,  with  the  view  of  ascertaining  the  rela- 
tive proportions  of  cotton  and  acid,  together  with  the 
proper  time  of  maceration  necessary  to  produce  a 
cotton  which  should  combine  the  largest  yield  with 
the  highest  explosive  power  and  solubility. 
The  following  formula  was  at  length  adopted: 

Eaw  cotton,         -         .         ,        .         g  p^^s. 
r^otassium  carbonate,        .        .        .        j     « 
Distilled  water,  -        .        .  -^i;^^     « 

Boil  for  several  hours,  adding  water  to  keep  up  the 
measure;  then  wash  until  free  from  any  alkali,  and 
dry.    Then  take  of— 

P^fied  cotton,        .        .        .        .        ^  oz.  av. 

JNitrous  acid  (nitric,  saturated  with  nitrous  acid), 

o  ?•  f  ^Z*^'         ■         -         -         -         4  pints, 
balphnnc  acid,  s.  g.  1.84,    -        -        .4      « 

Mix  the  acids  in  a  stone  jar  capable  of  holdino-  2  gals 
and  when  cooled  to  about  80°  Fahr.,  immerse  the  cot-' 
ton  m  small  portions  at  a  time ;  cover  the  jar  and 
allow  to  stand  4  days  in  a  moderately  cool  place  (temp 
50°  to  70°  Fahr.)  then  wash  the  cotton  in  small  por^ 


ning  unaf- 
ly  greater, 
nployment 

I  given  to  a 
3tton  in  a 
ether. 

1  a  number 
g  the  rela- 
r  with  the 
produce  a 
f^ield  with 

ted: 

2  parts. 
1      « 

)      « 

Bp  up  the 
Ikali,  and 

oz.  av. 
acid), 
:  pints. 


g  2  gals., 
!  the  cot- 
3  jar  and 
!e  (temp, 
lall  por- 


CELLULOSE. 


209 


tions,  in  hot  water,  to  remove  the  principal  part  of  the 
acid;  pack  in  a  conical  glass  percolator,  and  pour  on 
distilled  water  until  tlte  washings  are  not  affected  by 
solution  of  barium  chloride. 

Collodion,  on  spontaneously  evaporating,  forms  a 
transparent  and  impermeable  membraneous  coating, 
and  is  much  employed  in  photography,  also  somewhat 
in  surgery. 

Cellulose  is  attacked  by  chlorine;  the  use  of  solu- 
tions of  chloride  of  lime,  and  of  chlorine,  in  large 
quantities  in  washing,  or  bleaching,  will  cause  a  rapid 
deterioration  of  linen  or  cotton  goods. 

Schweizer  has  shown  that  cotton,  paper,  etc.,  is 
very  easily  dissolved  by  an  ammoniacal  solution  of 
copper.  Attempts  by  the  author  to  employ  this 
solution  for  a  *' water-proof  "  coating  of  fabrics,  as  has 
been  suggested,  failed  to  yield  a  satisfactory  result,  on 
account  of  the  liability  of  the  coating  to  crack  and 
peel  off. 

Peligot  has  found  in  the  skin  of  silk  worms,  and 
Schmidt  has  discovered  in  the  envelopes  of  the 
Tunicates,  a  substance,  tuniome,  which  has  the  com- 
position and  properties  of  cellulose. 

Linen,  hemp,  cotton,  wood  and  paper  are  all  essen- 
tially cellulose. 


n 


210 


ORGANIC    CHEMISTRY. 


AMYLACEOUS  SUBSTAN'CES. 

These  substances  are  almost  universaUj  present  in 
plants;  particularly  that  known  as  starch  or  femla. 

The  potato  yields  about  20  per  cent,  of  starch.  In 
order  to  obtain  it,  this  root  is  grated  and  the  pulp 
placed  upon  sieves,  arranged  one  above  the  other,  and 
through  which  a  streana  of  water  flows. 

The  grains  of  starch  being  extremely  minute  pass 
through  the  meshes  of  the  sieve,  while  the  walls  of  the 
cells  remain  behind.  The  starch  is  washed,  drained,, 
and  dried,  first  at  ordinary  temperature,  afterwards  by 
the  application  of  a  moderate  heat. 

Btaeoh.  ^(CeHioOs)  probably  C^B.^0,,.  Flour 
contains,  besides  starch,  nitrogenous  substances,  de- 
nominated gluten;  this  gluten  is  capable  of  ferment- 
ing, whereupon  it  becomes  soluble,  while  the  starch 
remains  unaltered  and  insoluble.  Under  these  con- 
ditions  the  gluten  gradually  dissolves,  disengaging 
ammoniacal  compounds,  hydrogen  sulphide  and  other 
products  of  putrefaction. 

At  the  end  of  twenty  or  thircy  days,  the  gluten 
having  become  dissolved,  the  liquid  is  removed,  and 
the  starch,  washed  and  dried,  shrinks  into  columnar 
fragments,  which  are  readily  pulverized  by  gentle 
pressure. 


'  iTii-n  T  j^ 


:!ES. 

Ij  present  ia 
i  otfecula. 
f  starch.    In 
md  the  pulp 
he  other,  and 

minute  pass 
3  walls  of  the 
hed,  drained,, 
fterwards  by 

)0i5.  Flour 
)stance8,  de- 
I  of  ferment- 
e  the  starch 
r  these  con- 
disengaging 
ie  and  other 

the  gluten 
irnoved,  and 
o  columnar 

by  gentle 


STARCH 


211 


A  more  modern  method  is  that  employed  in  France, 
which  is  essentially  the  same  as  the  process  cited  above, 
as  that  used  in  making  potato  starch  here.  The  water 
carries  away  the  starch  while  the  gluten  remains  be- 
hind in  the  form  of  an  elastic  mass,  which  is  also  util- 
ized. For  this  purpose  it  is  incorporated  with  flour 
poor  in  gluten,  to  be  made  into  macaroni,  and  for  the 
manufacture  of  a  very  nutritive  preparation,  "  granu- 
lated gluten;"  it  is  also  employed,  according  to  the 
recommendation  of  Bouchardat,  in  making  bread  for 
persons  afflicted  with  diabetes. 

Starch,  examined  with  a  microscope,  exhibits  flat- 
tened ovate  granules  of  different  size  in  various  plants, 
but  always  very  small.  Those  of  the  Eohan  potato 
have  a  length  of  0.185  mm.;  the  smallest  are  those  of 
the  Chenopodiwm,  quinoa  whose  length  is  0.002  mm. 

When  starch  is  heated  with  water  to  70°,  the  gran- 
ules increase  from  20  to  30  times  their  original  volume, 
and  become  converted  into  a  tenacious  paste.  A  small 
quantity  of  the  starch  passes  into  solution,  and  to  this 
the  name  amidin  has  been  given.  Starch  paste  and 
the  solutions  of  starch  have  the  characteristic  property 
of  becoming  bine  in  contact  with  small  quantities  of 
iodine.  The  liquid  becomes  colorless  at  about  70°,  but 
regains  its  color  on  cooling.  If  to  this  blue  liquid  a 
solution  of  a  salt,  sodium  sulphate  for  instance,  be 
added,  we  obtain  a  dark-blue  floculent  precipitate.  This 
substance,  called  starch  iodide,  is  not  a  chemical  com- 
pound, but  a  sort  of  lake,  containing  variable  quanti- 
ties of  iodine  difliised  throughout  the  starch  and  solv- 


212 


ORGANIC    CHEMISTRY. 


ent.  This  reaction  with  iodine  is  a  very  valuable  test 
for  starch,  but  is  open  to  several  fallacies,  and  apt  to 
mislead  in  inexperienced  hands. 

Until  lately,  it  has  been  claimed  that  starch  is  insol- 
uble in  water,  and  that  if  water  in  which  starch  has 
been  boiled  gives  with  iodine  the  characteristic  reaction 
of  this  substance,  it  is  due  to  particles  of  starch  suffi- 
ciently minute  to  pass  through  the  pores  of  the  filter. 
But  the  results  of  the  experiments  of  Maschke  and 
Thenard,  show  that  if  starch  is  heated  for  some  time 
at  100°,  it  is  partially  transformed  into  a  variety  solu- 
ble in  water.  This  substance  is  colored  by  iodine;  it 
furnishes,  on  evaporation,  a  gummy  solid  wliich  is  pre- 
cipitated by  alcohol  as  an  amorphous  powder. 

If  we  boil  starch  for  a  long  time  with  water  it  is 
<M)nverted  into  a  substance  called  dextrin.  The  pres- 
ence of  a  small  per  centage  of  sulphuric  acid  facilitates 
this  change,  which  is  soon  followed  by  the  transforma- 
tion of  the  dextrin  into  glucose.  The  sulphuric  acid 
is  not  at  all  altered  during  the  reaction. 

The  change  ot  starch  into  glucose  also  takes  place 
when  water  containing  starch,  and  to  which  germinated 
barley  has  been  added,  is  heated  to  about  70°. 

This  transformation  is  due  to  a  sulistance  called 
diastase  {from  Staffraffi?,  separation),  which  is  formed 
in  the  seed  during  germination.  The  production  of 
diastase  on  the  formation  of  the  young  shoot,  explains 
how  starch  becomes  soluble  and  serves  as  nutriment  to 
the  young  plant. 

The ptyalinot  the  saliva,  the  pancreatic  juice,  the 


y. 


ir 


STARCH. 


213 


able  test 
i  apt  to 

is  insol- 
irch  has 
reaction 
■ch  suffi- 
le  filter. 
;hke  and 
ne  time 
ety  solu- 
>dine;  it 
ill  ispre- 

ter  it  is 
'he  pres- 
iicilitates 
nstbrma- 
iiric  acid 

:es  place 
'minated 

!e  called 
8  formed 
iction  of 
explains 
iment  to 

nice,  the 


soluble  parts  of  beer  yeast,  gluten,  and  many  other  sub- 
stances, are  capable  of  producing  this  transtormation 
of  starch  into  dextrin  and  glucose. 

It  has  generally  been  considered  that  the  molecule 
of  starch,  in  being  transft)rmed  into  glucose  simply 
united  with  one  molecule  of  water  directly,  thus: 

C,Hio05+H80=C6HiA. 

MusculuB,  however,  claims  to  have  established  that 
the  starch  is  first  transformed  into  a  soluble  metamer 
and    this,  thereupon,   splits    up    into  dextrin    and 

glucose: 

C„H3oOi5+H20=2CeH,o05+CeHjA^ 


Dextrin. 


— v^ 
Olncose. 


By  further  action,  the  whole  of  the  dextrine  becomes 

converted  into  glucose,  (2-[3]60-203).  .     ^       ^  , 

Starch,  heated  simply  to  about  160°,  is  also  changed 

into  dextrin. 

It  is  attacked  by  dilute  nitric  acio,  mtrous  vapors 
are  given  off  and  difPerent  substances  are  produced, 
chiefly,  however,  oxalic  acid. 

If  starch  is  agitated  with  fuming  nitric  acid  it  is 
dissolved  and  water  precipitates  from  the  solution  a 
nitrous  compound  which  is  explosive. 

The  alkalies,  in  concentrated  solutions,  when  heated 
with  starch  disorganize  and  dissolve  it  Solutions  con- 
taining  t^o  to  three  per  cent,  of  alkali,  accelerate  the 
formation  of  starch  paste. 


214 


ORGANIC   CHEMISTRV. 


Starch  is  employed  in  the  laundry  and  therapentio- 
ally  in  poultices,  injections  and  baths. 

Tajaioca  is  the  starch  of  the  root  of  the  Jatropa 
manihoty  called  cassava  or  manioc. 

Sago  is  obtained  from  the  pith  of  various  sago 
palms. 

Arrow-root  is  the  starch  of  the  Maranta  arundi- 
nacew,  and  one  or  two  other  tropical  plants. 

Salep  is  obtained  trora  the  Orohts  masoula. 

Inulin.  There  has  been  found  in  the  roots  of  the 
Jerusalem  artichoke,  of  the  chicory,  and  the  bulbs  of 
the  dahlia,  a  substance  isomeric  with  starch,  called 
inulin. 

LicHENiN.  There  is  extracted  from  certain  lichens 
and  mosses  a  substance  called  Uohenin,  which  has  the 
property  of  swelling  in  cold  water  and  of  being  dis- 
solved in  boiling  water.  It  is  prepared  by  treating 
Iceland  moss  with  ether,  alcohol,  a  weak  solution  of 
potassa,  and  finally  with  dilute  hydrochloric  acid. 

There  exists  in  the  animal  organism  a  variety  of 
starch  designated  by  the  name  of  glycogen. 


DEXTRIN,  OB  DEXTBINE:. 

CjHioOs. 

To  prepare  dextrin,  starch  may  be  heated  with 
water  containing  a  small  quantity  of  sulphuric  or 
oxalic  acid  ;  the  operation  should  be  arrested  when 
the  liquid  gives  with  iodine  only  a  wine-colored  re- 
action. 


FLOUB 


215 


apentio- 
Tatropa 
lis  sago 
xrundi- 


i  of  the 
bulbs  of 
1,  called 

lichens 
has  the 
ng  dis- 
;reating 
ition  of 
id. 
riety  of 


d  with 
ario  or 
1  when 
red  re- 


For  the  acids,  a  small  quantity  of  germinated  bar- 
ley may  be  substituted,  placed  in  a  bag  immersed  in 
the  liquid.  Dextrin  thus  prepared  always  contains 
glucose.  It  may  be  obtained  free  from  this  substance 
by  heating  starch  with  i  its  weight  of  water  and  Tiftnr 

of  nitric  acid. 

Dextrin  is  amorphous,  slightly  yellow,  very  soluble 
in  water,  insoluble  in  alcohol  and  concentrated  ether. 

It  is  used  somewhat  in  preparing  bandages  in  case 
of  fracture,  and  very  extensively  as  a  paste  for  calico- 
printers. 

Dextrin,  forms  viscid  adhesive  solutions  which  are 
used  for  the  same  purposes  as  gum-arabic.  The  mu- 
cilage used  bv  the  U.  S.  government  for  postage 
stamps  is  composed  of  dextrin  two  ounces,  acetic 
acid  one  ounce,  water  five  ounces,  alcohol  one  ounce. 
Dextrin  may  be  distinguished  from  gum-arabic  by 
not  being  precipitated  on  adding  a  dilute  solution  of 
lead  acetate,  and  by  furnishing  with  nitric  acid  a  so- 
lution of  oxalic  acid  and  not  a  precipitate  of  mucic 
acid. 

FLOUE. 

Amylaceous  substances  are  of  great  importance  as 
food.  Wheat  and  other  cereals  are  the  most  import- 
ant sources  of  these  aliments. 

Starch,  as  also  sugar  and  the  neutral  carbohydrates, 
are  respiratory  foods  whose  principal  effect  is  the  pro- 
duction of  heat  by  being  oxidized,  or  burned,  in  the 
body. 


216 


ORGANIC   CHEMISTRY. 


The  composition  of  four  of  the  leading  cereals  i& 
herewith  given : 


1 

GB 

Dextrin 

and 
Olncose. 

o 

a 

1 

II 

Pi 

f 

OD 

h 
II 

Wheat,  14.0 

59.5 

7 

1.7 

14 

1.2 

1.5 

Rye,      16.0 

57.5 

10 

3.0 

9 

2.0 

2.0 

Oats,     14.0 

63.5 

8 

4.0 

12 

5.5 

4.0 

Rice,     14.5 

77.0 

0.5 

7 

0.5 

0.7 

Tlie  sticky,  elastic  substance  found  with  starch  in 
flour  is  gluten  (called  also  glutin),  and  is  a  mixture 
of  \ariou8  proximate  compounds  but  chiefly  of  three; 
legvimin,  or  vegetable  casein,  fibrin  and  gelatine. 

I'lour  of  good  quality  is  dry  and  soft  to  the  touch; 
it  f  jrms  with  water  an  elastic,  non-adhesive  dough. 

The  value  of  flour  depends  largely  upon  the  gluten 
it  contains,  though  not  as  stated  in  most  authors  upon 
the  percentage  of  this  substance,  but  upon  the  quality 
rather,  as  shown  by  recent  investigations  of  R.  W. 
Kunis  (26-74-1487). 

The  modern  "  patent  process,"  originating  in  Min- 
nesota, is  mainly  a  method  of  grinding  which  intro- 
duces into  the  flour  more  gluten  than  in  older  pro- 
cesses. 

GUM. 

CeHioOs. 

This  substance  is  very  widely  distributed  in  the 
vegetable  kingdom.     Gums  either  swell  in  water  or 


1 


OTTM. 


217 


ireals  is 


arch  in 
nixture 
r  three; 
le. 

J  touch; 
ugh. 
s  ghiten 
rs  upon 
quality 
K.  W. 

in  Min- 
1  intro- 
er  pro- 


in  the 
ater  or 


are  dissolved,  imparting  to  it  a  mucilaginous  consis- 
tency. 

From  a  chemical  standpoint  they  are  essentially 
characterized  by  giving  a  precipitate  of  muoic  acid 
on  being  boiled  with  nitric  acid,  and  by  precipitating 
lead  subacetate. 

Gum-arabic,  araiiin.  This  gum  exudes  from  dif- 
ferent species  of  acacias,  as  Acacia  arabica,  A.  sene- 
galensis,  A.  vera ;  it  is  obtained  from  Arabia  and 
Senegal. 

According  to  Fremy,  gum-arabic  is  a  salt  formed 
by  the  combination  of  an  acid,  gtimmic  or  arahio  acid., 
with  lime  and  potassa.  This  acid  may  be  isolated  by 
pouring  hydrochloric  acid  into  a  solution  of  gum,  and 
adding  alcohol;  an  am phorous  deposit  is  formed  which, 
dried  at  120°,  has  the  formula  CgllioOg.  This  acid  is 
very  soluble  in  water.  Its  solution  is  levogyrate,  like 
that  of  gum-arabic.  On  being  heated  to  150°  it  is 
transformed  into  a  substance  insoluble  in  water  called 
meta-gummic  acid,  whose  salts  are  likewise  insoluble. 
Gum-arabic  gives  with  ferric  salts  an  orange-colored, 
floculent  precipitate  soluble  in  acids. 

Ceeasin.  The  gum  which  exudes  from  cherry  and 
plum  trees  is  a  mixture  of  soluble  gummates  and  in- 
soluble meta-gummates;  hence  it  is  only  partially 
soluble  in  water. 

Cerasin  becomes  soluble  on  being  boiled  with  water, 
as  the  meta-gummates  ai-e  transformed  into  gummates 
by  the  action  of  boiling  water. 

These  gums  heated  with  dilute  sulphuric  acid  furnish 
a  dextrogyrate  sugar. 


1 


218 


ORGANIC    CHEMISTRY. 


Gum-tragacanth  often  contains  starch. 

Mucilage  or  Bassorin.  There  exists  in  the  seeds 
of  the  quince  and  flax,  in  the  roots  of  the  marsh-mal- 
low and  in  portions  of  many  other  plants,  a  substance 
or  substances,  which,  exposed  to  the  action  of  boiling 
water,  fnniich  a  thick  mucilage,  which  appears  to  con- 
sist of  a  soluble,  together  with  an  insoluble  substance. 
Nitric  acid  converts  this  mucilage  into  mucic  and  ox- 
alic acids.  Gum  and  mucilage  are  frequently  em- 
ployed as  emollients,  and  in  syrups,  also  extensively 
in  confectionery. 

Pectin  Group.  Many  roots,  as  the  carrot,  beet, 
etc.,  also  green  fruits,  contain  a  neutral  gelatinous 
substance,  insoluble  in  water,  alcohol  and  ether,  called 
pectose.  It  is  that  which  gives  to  green  fruits  their 
harshness.  Tliis  substance  is  modilied  during  the 
ripening  of  the  fruit  and  becomes  soluble,  vegetable 
jelly,  or  pectin  (from  nrjKTii,  a  jelly),  to  which 
Freray  assigns  the  formula  CajH48082. 

Pectin,  submitted  to  the  action  of  a  ferment  found 
in  1h9  cellular  tissues  of  vegetables,  called  pectase,  or 
of  cold,  very  dilute,  alkaline  solutions,  is  changed  into 
a  gelatinous  acid  called  pectosio  aoid,  then  into 
another  substance  likewise  gelatinous,  which  is  known 
by  the  name  of  pectio  aoid.  All  these  substances  are 
amorphous,  and  non  nitrogenous.  Their  formulae  are 
not  yet  definitely  determined. 

According  to  Fremy,  to  whom  we  are  indebted  for 
the  foregoing  facts,  the  jelly  obtained  from  the  current 
and  other  fruits  is  due  to  the  action  of  the  pectase  on 
the  laectin  of  these  fruits. 


LEOUMIN. 


219 


)  seeds 
ih-mal- 
tstance 
l)oiling 
to  con- 
istance. 
\nd  ox- 
ly  em- 
asively 

t,  beet, 
itinous 
,  called 
ts  their 
ng  the 
getable 
which 

t  found 
iase,  or 
fed  into 
m  into 
known 
ices  are 
alee  are 

3ted  for 
current 
ctase  on 


These  substances  resemble  gums  in  producing,  on 
boiling  with  nitric  acid,  a  precipitate  of  mucic  acid. 

Much  doubt  still  exists  respecting  the  composition 
of  the  pectin  group. 

LEGUMIN  OR  VEGETABLE  CASEIN. 

Legumin  is  found  in  most  leguminous  seeds,  such 
as  sweet  and  bitter  almonds,  also  in  beans,  peas,  etc., 
the  latter  containing  about  25  per  cent.  It  is  con- 
sidered to  be  identical  with  casein  by  Liebig  and 
"Woehler. 

It  may  be  obtained  by  digesting  coarsely  powdered 
peas  in  cold  or  tepid  water  for  two  hours,  allowing 
the  starch  and  fibrous  matter  to  subside,  and  then 
filtering  the  liquid.  It  forms  a  clear,  viscid  solution, 
which  is  not  coagulated  by  heat  unless  albumen  is  also 
present,  but,  like  emulsin  and  unlike  albumen,  it  is 
precipitated  by  acetic  acid.  It  is  coagulated  by  lactic 
acid,  also  by  alcohol;  in  the  latter  case  the  precipitate 
is  redissolved  by  water. 

Acetic  acid,  diluted  with  8  to  10  parts  of  water,  is 
-arefully  dropped  into  the  filtered  solution  obtained 
above,  and  the  legumin  is  precipitated;  an  excess  of 
the  acid  should  be  avoided,  as  this  would  dissolve  th*o 
precipitate.  It  falls  in  the  shape  of  white  flakes,  and 
after  having  been  washed  on  a  filter  should  be 
dried,  pulverized  and  freed  from  adhering  fat  by 
digestion  in  ether.  Legumin  may  be  obtained  from 
lentils  with  the  same  facility  as  from  peas;  but  it  is 


220 


ORGANIC    CHEMISTRY. 


less  easily  procured  from  beans  (haricots),  in  con- 
sequence of  their  containing  a  gummy  matter  whicli 
interteres  with  its  precipitation  and  with  the  filtration 
of  the  liquids. 

The  cnemical  properties  of  legumin  are  identical 
with  those  of  casein. 

Liebiar  supposes  that  grape-juice  and  other  vegetable 
juices  which  are  deficient  in  albumen,  derive  their 
fermentation  power  from  soluble  legumin.  This 
principle  is  soluble  in  tartaric  acid,  and  to  its  pi  i:sence 
he  ascribes  the  tendency  of  sugar  to  toim  alcoliul  and 
carbon  dioxide  instead  of  mucilage  and  lactic  a^jd. 

VEOETTABLE  ALBUMEN. 

Vegetable  albumen  is  contained  in  many  plant- 
juices  and  is  deposited  in  floccuU  on  applying  heat  to 
such  liquids.  It  can  also  be  f -(.ipltated  by  nitric 
acid,  tannin  and  mercurio  cliloride  brecisely  tikeanimal 
albunicn.  Vegetable  albumen  is  composed  of  carbon, 
hydrogen,  nitrogen,  oxygen  and  sulphur.  There  is  no 
trustworthy  formula  for  this  substance. 


con- 
which 
ration 

mtical 

;etable 

I  their 

This 

ui  and 
^id. 


plant- 
beat  to 

nitric 
animal 
»rbon, 
■e  is  no 


mfmMK 


INDEX. 


PAOE. 


86 

129 

18 


Acenapthene,  CnUu)— 154..  38 
Acetamide,  d  Ih  NO=S9-  •  '36 
Acetanilide,  Cs  II»  NO=i3S.  130 
Acetic  oxide  C4  He  Os  =io3  103 

Acctochlorhydrlc  glycol 63 

Acetone,  C3  H«  0=e,S. . .  .99,  108 
Acetyl  acetate,  C4  N9  Os  . . .  103 
Acetyl  chloride,  CjClHsO.  103 
Acetyl  hydride  or  aldehyd 

C2H4  0=44 '■■■ 

Acetylatninc,  C2  H5  N=43.. 

Acetylene,  Ca  H2  =26 

Acety lide,  cuprous 19 

Acid.acetic,  C2  H4  O5  =60. .  99 
Acid,  aconitic,  C«  He  Oc  =95  174 
Acid,  acrylic,  Cs  H4  Oa  =72.  9' 
Acid,  adipic,  Ce  H10O4  =148  9' 
Acid,alloxanic,C4H4N2  05  125 
Acid.alphacymic,  CiiHuOa  91 
Acid,  amalic,  Ce  H7  Na  O4  . .  169 
Acid,  anchoic,  C9  HieOi  =188  93 
Acid,  angelic,  C3  Hg  O2  =108  91 
Acid,  anisic,  Cs  Hb  Os  =  1 5^-  92 
Acid,  arable,  Ce  H10O5  -34^  2>7 
Acid,  arichidic,  C20H10O2  •  •  9" 
Acid,  atropic.Cs  Hg  Oa  =148  164 
Acid,  benzoic.CT  He  O2  =  126 

91,  109, 126 

Acid,  benzoglycolic 126 

Acid,  butyric,C4  H9  Oa  . .  9°.  »o8 
Acid,  caffetonnic >96 


95 
II 

33 
32 
92 


PAOE. 

Acid,camphic,  CioHieOao=9'  168 
Acid,  campholic,  C19H18O4  •  •  9' 
Acid,  camphoric,CioHi804  41,  93 
Acid,  caprylic,  Cs  HieOa  •  •  ■  9° 
Acid,  caproic,Ce  HiaOa  =  1 16  90 
Acid,  capric,  CioHaoOa  =  172  9° 
Acid,  carballylic,  Ce  Hs  Oa  . 
Acid,carbamic,  CIIs  NO2  .  • 
Acid,  carbazotic,(  Picric) 

CHsNs  07=229 

Acid,  carbolic.Ce  He  0=94. 
Acid,carbonic,Ca  Hs  0=62. 

Acid,  catechic 196 

Acid,  cerotic,  C27HMO...90,  180 
Acid,  chelidonic,  C7  H4  Oe  •  •  95 
Acid,  chlorbenzoic.C;  H5  CIO 

=  130.5 '60 

Acid,  cholalic,  C21H40O5  =408  g^ 
Acid,  cholesteric,  Cs  H 10O5  •  •  95 
Acid,choloidic,CaiH3804  =  39o  94 
Acid,  cinnamic,  C9  Hg  O3  = 

148 9'.  J" 

Acid.citraconic  C5  He  O4  93.  '21 
Acid,  citric,  Ce  Ha  O7.  Ha  O = 

19J-4-18 120,  95 

Acid,  coccinic,  CisHseOa  ...    90 
Acid,  comcnic,  Ce  H4  O5  • . .     95 
Acid,  coumaric,  C9  Hg  O3  . . 
Acid,  croconic,   C5  H2  O5  . . 
Acid,  crotonic,C4  He  Oa  ..91. 
Acid,  cuinic,  CjoHiaOa  =  164 


93 

95 
178 

91 


II 


222 


INDEX. 


PAGE. 

Acid,  cyanacetic, 

CaHs(CN)  03=85 103 

Acid,cyanhydric,HCN  =  27.   161 

Acid,dextroracemic 117 

Acid.dialuric,  C4  H4  Nj  O4  135 
Acid,  dinitrobenzoic, 

CTH4(NO!j>i02=52i2..,  no 
Acid,  doeglic,  C19M36O2  =  296  91 

Acid,  elaidic 177 

Acid,  erucic,  C22H4202  =338.  91 
Acid,  ethaliCiCieHaaOj  =256  179 
Acid,  ethj'Isulphuric, 

CaH6HS04=i26 71 

Acid,  formic,  CH2  O2  =50.98,  90 
Acid,  fumaric,C4  H4  O4  =  1 16  93 
Acid,  gallic,  C7  He  O5  .  -95.  »97 
Acid,  glucic,  Cia  Ha  O9  =306  186 
Acid,  glyceric,  C3  H«  O4 . . .  93 
Acid,  glycolic,  C2  Hi  Os  .60,  92 
Acid,  guaiacic,  Ce  Hg  O3  . . .  92 
Acid,  gummic,  C12  H22  On..  217 
Acid,  hippuric,  C9  HjNOs..  125 
Acid,  insolinic,  C9  Hs  O4  . . .  94 
Acid,  itaconic,  C5  He  O4  . .  121 
Acid,  lactic,  CsHeOs-.g^.  "2 
Acid,  lauric,  Ci2Ha402  =200  90 
Acid,  leucic,  C«  H^Os  =  132.  92 
Acid,  lichenstearic,  C9  HuOs  92 
Acid,  nthic,  C5  H4  N4  O3  . .  123 
Acid,  lithofelUc,  CaoH88P4  . .  93 
Acid,  malic,  C4  Hj  Os  =134  ^'S 
Acid,  malonic,  Ca  H4  O4  . . .    93 

Acid,  mannitic 183 

Acid,  tnargaric,  CnHs402  ...  I77 
Acid,  meconic,  Cj  H4  O. . . .  143 
Acid,  melissic,    CaoHgoOa  . .    90 


PAGE. 

Acid,  tnellitic,  C4  Ht  O4  . . . .  94 

Acid,  mesoxalic,  C3  H2  Os  . .  94 

Acid,  tnetagummic 217 

Acid,  monochloracetic, 

Ca  CI  H3  Oa  =945 aoi 

Acid,  moringic,  Ci5H2a02  . .  91 

Acid,  morintannic 196 

Acid,  mucic,  Ce  Hj  Og  =  205  95 

Acid,  myristic,  CuHagO-^ ...  90 

Acid,  cenanthalic,  C7  HuOa  90 

Acid,  cenanlhic,  Ci4H2g03  . .  92 

Acid,  oleic,  Ci8H3403  =282.  91 

Acid,  opianic 127 

Acid,  oxalic,  Ca  Ha  O4  ■  .93,  1 12 

Acid,  oxamic,  Ca  H3  NO3  . .  11 

Acid,  oxybenzoic,  C7  He  O3  195 

Acid,  oxybutyric,  C4  Ha  O3  92 

Acid,  oxycuminic,  CioHjaOa  92 

Acid,oxynapthalic,  CioHe  O4  94 

Acid,  oxy valeric,  C5  H10O3  . .  92 

Acid,  palmitic,  CieHaaOa  .90,  177 

Acid,  parabanic,C8  Ha  N2  Os  125 

Acid,  paraflnic,  C24H4802  . .  23 

Acid,  paralactic 123 

Acid,  paramalic,  C4  H4  O4  . .  116 

Acid,  paratartaric 117 

Acid,  pectic,  C16H22O5  =294.  2i8 

Acid,  pectosic 218 

Acid,  pelargonic,  C9  H18O2  ...  90 

Acid,  phenic,  Ce  He  0=94 . .  33 
Acid,  pheny  Isul  phuric, 

Ce  He  048=174 33 

Acid,  phloretic,  C9  HioOa  . .  93 

Acid,  phtaliCjCa  He  O4  =  150  94 

Acid,  phy8etoric,CieH9oOa ..  91 

Acid,  picric,  Ce  Hs  (NO2  )3  O  33 


PAGE. 

•  94 
••    94 

•  317 


.... 

aoi 

2  •• 

9« 

196 

20S 

95 

)... 

90 

Oa 

90 

s  .. 

92 

82. 

91 

127 

•93. 

112 

3  •. 

II 

O3 

'95 

Os 

92 

jOs 

92 

5O4 

94 

>3.. 

9^ 

93 

177 

Os 

125 

2  •• 

23 

132 

1  •• 

116 

117 

294. 

218 

•    .    - 

218 

)2.. 

90 

H-- 

33 

•  ••• 

3a 

»  •• 

92 

150 

94 

h.. 

91 

)3  0 

33 

INDKX. 


223 


PAOE. 

Acid,  pimelic,C7  H1JO4   93 

Acid,  pinaric,C,»)H;ii02  =302  41 

Acid,  pinic,  Caol  I:»02  =  302 . .  91 

Acid,piperic,Ci2Hio04  =218  94 
Acid,  propionic,  C3  Hu  Ox  78,  90 

Acid,  prussic,  nCN=27.    ..  «6i 

Acid,  pyrognllic,  Ce  He  O3  .  198 


PAOC. 

Acid,  thionuric, 

C4HbN03S03=J95---  "S 
Add,  thymotic,  CnHuOs  ••  9^ 
Acid,  toluic,  Cs  Ha  O2  =  13^'  9' 
Acid,  trichloracetic, 

HGj  CI3  Oa  =  163.5 102 

Acid,  tropic,  C9  HioOs  =166.  164 


Acid',  pyroligneous 100    Acid,  uric.Cs  H4  Ni  O3  =  168  123 

Acid,pyroineconic,C5H4  08    92  |  Acid,  valeric  or    valerianic. 
Acid,  pyrotartaric,  C5  Hg  O4 

=  132 93.117 

Acid,  pyroterebic,C6  H10O2  .  •  9' 
Acid,  pyruvic,  C3  H4  O3  -88  92 
Acid,  quinic,  C7  HiaOe  =144-    93 

Acid,  quinotannic 19^ 

Acid,raceniic,C4  He  Oe  =15°  "7 
Acid,  ricinolcic,  Ci8H3403,92.  180 
Acid,  roccellic,  CnH3204  .  •  93 
Acid,  salicylic,  Ct  H5  Os  i95.32.92 

Acid,  sarcolactic '22 

Acid,  scammonic,  CisH-^Os  92 
Acid,  sebic,  C10H18O4  =202..  93 
Acid,  sorbic,  Co  U%  Oa  =112.  9« 
Acid,  stearic,  C18H36O2  .  .90.  '77 
Acid,  8uberic,C8  H14O4  =  1 74  93 
Acid,  succinic,  C4  IIe04  93.  »i5 
Acid,  sulphocarbolic, 

C6H6S04=i74 33 

Acid,  sulphoglucic 185 

Acid,  sylvic,  C20H90O2  =  302.  41 
Acid,  tannic,  C27H220i7=6i3  196 
Acid,  tartaric.Ca  Ho  0«  .  ..116,  95 
Acid,  tartrelic,  C4  H4  O5  . . .  "7 
Acid,  tartronic,  C3  H4  O5  . .  94 
Acid,  terebic,CT  H10O4  =  158  93 
Acid,  terechrysic,  Ce  He  O4     94 


CeHic02=io2 109,  90 

Acid,  veratric,  C9  HioOs  ...    94 
Acid,  xylic,  C9  H10O2  =  150-     9' 

Acids 95 

Acids,  aromatic 9' 

Acids.fatty 90 

Acids,  general  methods  of 

preparation, 9" 

Acids,  organic 9^ 

Acids,  defined..... 95 

Acids,  polyatomic 112 

Acids,  pyro 97 

Aconitina,  C30H47NO7  =533-  1^5 
Alcohol,  allyl,  C3H6O...45,  57 
Alcohol,  amy  lie,  C5Hi20.56,45 
Alcohol,  benzyl,  Ct  Hs  0=  108 

46 

Alcohol,  butyl,  C4  HioO=64  45 
Alcohol,  eery l.CflHseO = 396    45 

Alcohol,  cholesteryl 4^ 

Alcohol,  cinnyl,  C9H10O..    46 

Alcohol,  cuneol 46 

Alcohol,  cymol,  CjoHuO..  46 
Alcohol,  melissic,  CaoHjaO . .  180 
Alcohol,  methyl,  CH4  O.  .45,  46 
Alcohol,  myricyl,  CsoHeaO..  45 
Alcohol, octyl,  Cs  HwOs  130    45 


224 


INDEX, 


FAGZ. 

Alcohol,  ordinary,  or  ethyl, 

C2  He  0=46 49 

Alcohol,  propyl,  Cs  Hg  O.. .  45 
Alcohol,  sexdecyl,  C16H34O. .     45 

Alcohol,  sextyl,  Ce  HuO 45 

Alcohol,  vinyl,  C2  He  0=46  45 
Alcohol,  xylyl.Ca  HioO=  122    46 

Alcohols,  diatomic 58 

Alcohols,  monatomic 44 

Alcohols,  polyatomic 59 

Alcohols,  sulphur 82 

Alcohols,  selenium 8; 

Alcohols,  tellurium 82 

Alcohols,  tetratomic 59 

Alcohols,  triatomic 64 

Aldehyds 86 

Alizarin,  CioHe  Os  =  174. . .     39 

Alkalaniides 136 

Alkaloids 127 

Allantoin,    C4  He  N4  Os  =  158 

124 

Alloxan,  C4  H4  N2  O5  =160.  125 
Alloxantin,  Cg  H10N4  Oio. .  123 
Allyl  iodide,  Cg  H5  1=  i63. .  57 
Allyl  sulphide,  Ce  IIioS=  114  57 
Allyl  sulpho-cyanide, 

C4H5NS=99 57 

Allylamine,  Cs  H7N=:57,..   127 

AHylene,  C3  H4  =40 20 

Amane,  Cs  Hi2=72 23 

Amber 26,  42 

Amides 136 

Amidoxypropyl, 

C3H4(I;H2)0=72 75 

Amines 133 

Ammelide 172 


PAGE. 

Ammonia  aldehydate, 

C3H4  0NH3=6i 87 

Ammonia  citrate  of  iron. ..  121 

Ammoniacum 43 

Ammonias,  compounds 131 

Ammonium,  cyanate,CH4  N2  172 

Ammoniums 137 

Ammoniums,  quarternary. .   136 

Amygdalin,  CjoHijrNOn 193 

Amyl,  acetate,  C7  HuOs  . .  5^ 
Amyl,  chloride,  C5H11CI..  56 
Amyl,  hydride,  C5  Hi2=  72.  23 
Amylamine,  C5  Hi3N=87. .   121 

Amylene,  C5  Hio=  70 23 

Anhydride,  tartaric, 

C4H4  0s=i32 117 

Aniline 30,  127,  131 

Anthracene,  Ci4Hio=  178.  .29,  39 

Arabin  Ci2H220n=342 217 

Arbutin  CisHi607  =284. ...  193 
Aricina  C2SH26N2  O4  =397. .   129 

Arnicin 42 

Aromatic  compounds 89 

Arsines 128 

Asphalt 26 

Assafoelida 43 

AtropiaCnHjsNOs  =289. 164,129 

Balsams 41 

Bases  organic, 125 

Bases  quarternary, 136 

Bassorin 218 

Belladona 164 

Benzene  C«  He  =78 27 

Benzine 24 

Benzoic  aldehyd,  C7  He  O..  86 
Benzol,  Ce  Hj  =78 27 


87 

1. .. 

121 

... 

43 

131 

4  Na  172 

. . . . 

137 

ry.. 

136 

193 

3.. 

56 

:i.. 

.S6 

=72. 

23 

57.. 

121 

... 

23 

117 

127. 

131 

!•  -29.  39 

... 

217 

... 

193 

>7-- 

129 

42 

89 

* .  ■ 

128 

26 

43 

.  164,129 

... 

41 

. .  • 

125 

. .  • 

136 

.  ■ . 

218 

... 

164 

... 

37 

24 

0.. 

86 

27 

INDEX. 


226 


PAGB. 

Benzone,  C0(C6  H5  )2  =  182  1 19 
Benzonitrile  C7  H5  Nsiog..  no 
Benzyl  chloride,  Q  H5  O  CI  126 

Benzylene,  Ci5n28=  208 20 

Bidecane,  Ci2H»=  1 7° 28 

Bidecy  1  hydride,  Ci2H26= « 7°    23 

Bitumen 26 

Biuret,  C2  O2  H5  N3  =  1 13  •  •   172 

Borneol,  CioHisO  =  1 54 5^ 

Brandy 52 

Brucia,  C23H28N  04,4H2  0 

=  394+72 161,  129 

Butane  C4  Hio=5S 23 

Butter 

Butyl  hydride,  C4  Hio=58. . 
Butylamine,  C4  HiiN  =  73. .. 
Butylene,  C4  Hs  =56. . .  .20, 

Cacodyl,  (CH  3)2  As 79, 

Caffeia  (caffeine), 

Cg  H10N4  0=  194 130.  168 

Campholic  alcohol 117 

Camphor,artificial,CioHi6HCl  37 
Camphor,  CioHi60=i52....  40 
Camphor,  monochlor, 

CioH5iC10=  186.5 41 

Camphor,  oxy-,  CioHieOj  ...  41 
Camphor  of  Bornco.CioHisO  58 
Cantharidin,  C5  Hg  O3  =95-   »<j8 

Candles, i?^ 

Cannabin...  42 

Caoutchouc,  (C5  Hg  )x 36, 43 

Caprylamine,  Cg  Hi9N=i29.  127 
Caramel,  CiaHigOg  ?=3o6..   190 

Caramelaae, 190 

Caramelene,  190 

Carameline, 190 


179 

23 

128 

23 
105 


PAOB. 

Carbo-hydrates,  defined,. ...      7 
Carbonic  ether,  C5  H10O3  . .     74 

Casein,  vegetable, 219 

Castor  oil, 180 

Castorin, 42 

Cellulose,  (cellulin,) 

(CisHaoOs) 20^ 

Cerasin 217 

Cetene,  CiiH22=  iS4 23 

Chitin 184 

87 


Chloral,  C2  CI3  HO=  147.5. 
Chloral  hydrate, 

C2  HCl+2HO=6o.5+63...  88 
Chloroform,  CHCI3  =  1 19-5-  47 
Chloropropyl.Ca  He  CI  =  77.5  1 5 
Cholesterophan,  C5  Ho  Ni  O3  169 
Cinchonia,  (cinchonine) 

CasHajNa  0=308 129, 156 

Cinchonicia,  (cinchonicine) 

C2oH2»N2  02=3o8 158 

Cinchonidia,  (cinchonidine) 

CaoH24N2  0=308 158,  129 

Cinnamene,  Cg  Hg  =  104 —     38 
Codeia,  C13H21NO3  =299.146,129 

Colchinia 163 

Collodion 208 

Colophony 41 

Compound  ammonias 131 

Conia,(conine),  C3H15N.141,  129 

Conicine,  Cgiri5N=i35 129 

Coniferin,  Ci6H2203  =342  . .  193 

Convolvulin,  CsiHjoOib 193 

Conylia,  Cg  Hi5N=  125 . .  141,  129 

Cotarnine i47 

Creamof  Tartar,  Ct  HsKOe  116 
Creatin,  C4  H9  Ns  Oj  =  131 .  188 


226 


INDEX, 


PAr.E. 

Creosote 34 

Cresylol,  C7  Hg  0=  108  ..  29,  34 

Crotonylene,  C,i  He  =54 20 

Cumene,  C9  Hi2=i2o, 28 

Cumidine,C9lIi3N=i35....  127 
Cuprous  acctvlide, 

CU1C4  1 120=319.6 20 

Curari 163 

Curarina 162 

Cyanopropjl,  C3  He  (CN). . .  15 
Cyclamin,  C2oH2iOio=424. .  193 

Cymene,  CioHi4=  134 28,  38 

Cyinogene, 24 

Cymol,  CioHi4=  134 4' 

Daphnin,  CsiHsjOn '93 

Daturia,  (atropia) 

CnHasNOs  =289 164, 129 

Decane,  CioHa=  142 24 

Dextrin,  Ce  HjoOr  =162.212,214 

Diastase 212 

Diethylamine,C4HuN=73.  128 
Diethj'lpropyl, 

Cs  H5  (C2  H5  )2  =99 IS 

Diethylenic  diamine, 

C4  HioNj  =86 170 

Digitalin 166 

Digitin 166 

Diinethylpho8phine,Ca  H;  P  128 

Draconyl 38 

Dulcite,  (dulcose) 

CeHuOe  =126 183,  181 

Duodccylene,  C12I lu=  168. .  23 

Elaidine i7S 

Elaine I7S 

Elayl,  C2  H4  =28 21 

Eletni 43 


PAGE. 

Emetia,  CisHjjNOj  =248. . .  167 

Emetics 119 

Ergotin 42 

Erythrite,  C4  H10O4 49 

Esculin,  CiiHiuOis 193 

Essence  of  mirbane, 

C:6H5NC)2=i23 29 

Essence  of  thyme,CioHie 34 

Essential  oil  of  cloves,CioH]e    37 

Essl.  oil  of  bergamot 37 

Essl.  oil  of  copaiba,  C2oHa2-  •  37 
Essl.  oil  of  cubebs,  CjoHffl.. .  37 
Essl.  oil  ofelemi,  CioHi6=  136  37 
Essl.  oil  of  juniper,  CioHie-  ■ .     37 

Essl.  oil  of  lemon,  CioHie 37 

Essl.  oil  of  orange,  CioHie. . .  37 
Essl.  oil  of  pf.'pper,  CioHie. . .     37 

Elhal,  Ci6Ha»02  =258 179 

Ethane,  C2  He  =30 13.  » 5.  23 

Ethene,  C2  H5  =29 13,  15 

Ether  acetic, 

C2  H5  C2  Hs  O2  =88 73 

Ether,  butyric,  Ce  H12O2  =11681 
Ether,  ch!  orhydric,  C2  H5  CI.  75 
Ether,  cor  imon,  C4  HioO= 74  70 
Ether,  cya  nhydric,  Cs  H5  N .     77 

Ether,  ethl,  C4  Hio=  74 70 

Ether,  formic,  Cs  He  O2  =174.  8i 
Ether,  hydroiodic,  C2  H5  I .  •  76 
Ether,  hydrosulphuric, 

C4HioS=90 83 

Ether,  ocnanthylic, 81 

Ether,  oxalic,  Ce  II10O4  =146  74 
Ether,  oxamic,  C4  H7  Os  N.  117 
Ether,  sulphuric,  C4  HjoO . .  70 
Ether,  valerianic, 81 


PAGE, 

167 

... 

119 

... 

42 

... 

49 

... 

»93 

29 

34 

EI]6 

37 

37 

Q.. 

37 

[... 

37 

136 

37 

... 

37 

37 

37 

37 

179 

,  »5 

.23 

••«3 

.IS 

•  •  • 

73 

=  11681 

CI. 

75 

=  74 

70 

N. 

77 

70 

174. 

81 

I.. 

76 

... 

83 

... 

81 

146 

74 

N. 

117 

3.. 

70 

•  ■  ■ 

81 

INDEX 


227 


PAGE. 

Ether,  vinic,  C4  HioO= 74.  •  •  7" 

Ethers 69 

Ethers,  simple 69 

Ethers,  compound 73 

Ethers,  miscellaneous 81 


Ethers,  mixed 38 

Ethine,C3H2=36 13 

Ethyl,  C2H5  =29 15 

Ethyl  chloride,  CaHsCl...  75 
Ethyl  cyanide,  Ca  H5  CN. . .  77 
Ethvl  formiate,  Ca  He  O2  . . .  9 
Eth'ylglycol,  C4  H9  Oj  =89.  61 
Ethyl-hcxyl  ether,  Cg  HisO..  84 
Ethylhydride  C2  II5  =30 .. .  23 
Ethyl  iodide,  Q  H5  I  =  1 56-  •  7^ 
Ethyl  mercaptan,  C4  He  S,..  83 
Ethylmethylaniline,  C9  H13N  30 
Ethyl  oxide  C4HioO=  14....  69 
Ethyl  sulphide  C4  HioS=9o..  83 
Ethylamine,  Ca  H7  N . . .  132, 127 

Ethylene,  CaH4=  28 21 

Ethylene  bromide,  Ca  H4  Ba 
Ethylene  chloride.Ca  H4  Cla 
Ethylene  oxide,  Ca  H4  O — 
Eucalin,  Ce  HiaOe  ~i8o. . . 

Fats 

Fatty  acid  series 

Fermentation,  acetic 100 

Fermentation,  alcoholic . .  49,  181 

Fermentation,  gallic i97 

Fermentation,  lactic 122 

Ferrocyanide  of  potassium, 

K4FeC6Ne=368 172 

Flour 21S 


61 

76 

62 

183 

174 
90 


Fulminates 54 

Fusel,  or  fousel  oil S** 

Galactose,  Ce  Hr^Oe  ....  187,  182 

Gas,  illuminating 21 

Gasolene 24 

Glucosane,  C«  IliaOe  =iSo  .  185 
Glucose,  Ce  HuOo  =  iSa  182, 184 

Glucosides 1921  184 

Gluten 216 

Glycerin,  Ca  H3  O3  =92 •  •  •  •    64 
Glycocol,  Zincic, 

Zn(C3H4N02)2  =213-2.  126 
Glycogen,  Ce  HiqOb  =162..  214 
Glycol,  amyl,  C5  H12O2  -  IC4  59 
Glycol,  butyl,C4  H10O2  =90-  59 
Glycol,  diethyl,  Co  Hi  1O2  . .  61 
Glycol,  ethyl,  C4  H9  Oa  =89  61 
Glycol,  hexyl.Ce  H4  Oa  =  1 18  59 
Glycol,  monochlorhydric. . . 
Glycol,  octyl.Cs  H13O2  =  146 
Glycol, ordinary,  C2  He  Oj  ... 
Glycol,  propyl,  C  sHs  O^  ,  58, 

Grape  sugar 182 

Guano "4 

Gum,  Ce  H10O5  =162 216 

Gum  arabic 217 

Gum  resins 4^ 

Gun-cotton 207 

Helicin,  C13H16O7  =283 '94 

Heptyl  hydride,  C7  Hi6=  100.    23 

Heptane,  C  7llie=  100 23,  24 

Heptylene,  C7  Hi4=98 22 

Hexadecane, Ci6Ha4=327---    24 
Hexadecyl  hydride,  CioHa*--     24 


62 

59 

59 

123 


Formene,Cll4=i6 '^    "«««««•  C«Hu= 86^- 23 

Frankincense 43 1  Hexylene,  Ce  Hia=84 22 


228 


INDEX. 


FACE. 

Uexyl  hydride,  Cc  Hi4=86..     23 

Hoffmann's  anodyne 73 

Homologous  series 12 

Honey 192 

Hydrides 23 

Hydrocarbons 18 

Hydrocarbides 18 

Hydrocarbides,  extra-terres- 
trial      40 

Hydrogen  carbides 18 

Hydrosulphuric  ether,C  4H10S  83 
7Iyosciamine,CnH23N08  129, 164 

J  ndigo 130 

Inosite,  (inosin)C6  HiaOe  187, 182 
Inuline,  Co  M10O5  =  162  ... .  214 

lodomorphia 145 

Isatin,  Cs  H5  NO2  =  147 ... .     38 

Isologous  series 12 

Isomerism 8 

Jalappine,  Cg4HMOi(i=7i6...  103 
Jerria,  C20H46N2O3  =362...   163 

Kerosene  . .- 24 

Ketones 40 

Lactide,  C3  114  Oj  =72 123 

Lactose  or  lactin, 

Ci2H240ij=342 191,  182 

Leatiier 197 

Legumin 219 

Levulosan,  Co  H10O5  =  162..  190 
LevuIose.Cs  HijOo  =  iSo.  187,182 

Lichenin 214 

Madder 39 

Maltose,  Ce  llviOa  =  iSo 182 

Mannitane,  Co  H12O5  =164..  183 
Mannite,  Cs  HuOo  =182.181,183 
Marsh-gas,  CH4  =16 23 


PACK. 

Meconine, 143, 147 

Melampyrite,C6  H14O  6=184  181 
Melezitose,  Ci2H220i8=374..   182 

Melitose,  Ci2H240i2=365 182 

Mercaptans 82 

Metamerism 9 

Metaterebenthene,  CjoHsj-  •     38 

Metastyrol, 38 

Methane,  CH4  =  16. . . .  13,  15,  23 

Methenyl,  CH=i3.   15 

Methyl,  CH3=  15 15 

Methyl  acetate,  Cs  He  O2  ...  9 
Methyl  chloride,  CH3  CI. . . .  47 
Methyl  cyanate,  C2  H3  NO..  131 
Methyl  hydride,  Cn4  =16..  23 
Methylamine,  CH5  N. .  .127,  131 
Methylethylamine,  C3  H9  N  128 
Methylphosphme,  CH5P...  128 
Methylpropyl,C8  He  (CUs  ).     1.5 

Molasses 189 

Monamines 133 

Monochlorcamphor, 

CioHi5C10=86.5 41 

Monochlorhydrin, 

C3H7C102=  iio-s 66 

Morphia,  (Morphine) 

C17H19NOJ  =285 143,  129 

Murcxide,C8  Hs  Ne  Oe  =284  125 
Mycose,  Ci2H220ii=342.. . .   182 

Naphtha 24 

Naphlhalamine,  CiqHq  N.  . .  128 
Naphthalin,  CioHg  =128..  .27,  38 
NarceJa,C2sH29NOa  =463.148,129 
Narcotina,  C22H23N07  =413  129 
Nicotina,  CioHi4N2  =162.139,129 
Nicotyl,  Cs  U7  =67 140 


PAOE. 

»3. 

«47 

H 

iSi 

, , 

182 

, 

182 

. 

82 

. 

9 

. 

38 

. 

38 

«s 

.23 

. 

15 

. 

15 

■. 

9 

. 

47 

).. 

i3« 

■. 

23 

7. 

13' 

N 

12S 

12S 

)• 

IS 

. 

189 

• 

»33 

• 

41 

• 

66 

t3. 

129 

H 

I2S 

. 

182 

. 

24 

, 

128 

27 

,38 

48 

,129 

3 

129 

39 

,129 

. 

140 

INDKX. 


229 


NicotyUa,CioHi4N2  =162.139,129]  Papaverine,  C'»H2iN04  .129,  148 

Paramorphia,  CisHaiNOj  . . .  148 
Paraniylene,  CioUa)=  140. . .  22 
Pectin 218 


Nitrile  bases '24 

Nitrobenzol,  Ce  Hs  NOj  ....     29 
Nitroglycerine, 

C3K5(N02)3  03=227...     66 
Nitrylsor  cyanhydric  ethers,  134 

Nonane,  C9  Ha)=  128 23 

Nonyl  hydride,  Cg  Hao=  128.     23 

Nonylene,  C9Hi8=i26 22 

Octane,C8lIi8=ii4 23 

Octyl  glycol,  Cg  HisOa  =  146    59 
Octyl  hydride,  Cs  Ht8=  1 14. .     23 

Octylene,  C8Hi6=ii3 22 

Oils,  fatty 174 

Oils,  essential 36 

Olein,  C5-H101  Oe  =884 i7,i 

"Oleomargarine" 179 

Oleo-resins 42 

Opium '42 

Orcin,  C7  Hs  O2  =  124 193 

Organizable  substances 205 

Organometallic  compounds,  78 
Oxamide,C2H4  0^X2=92,  74 
Oxanthracene,  C^Hg  O2  . . . .  39 
Oxycamphor,  CioHi«02  =  16S  41 

Para-arabin 192 

Plants,  respiration  of. 201 

Plants,  nutrition  of. 204 

Polyamines 170 

Polymerides 9 

Polymerism, 9 

Populin,  Ci»H2208  =390 '93 

Potassium,  binoxalate 1 14 

Potassium,  ferrocyanide, 

K4FoC6Nfi  =368 172 

Paraffin,  Cjj  H5  O = 33S . . . .  2  2  24 


Pectose 218 

Pentadecane  Ci5H32=  212...  24 
Pentadecyl  hydride,  QsHs-j.     24 

Petroleum 24 

Phenol,  Ce  H  60= 94 32 

Phenol,  potassic  Ce  H5  KO..  32 
Plienol,  trinitric 

Co  HsCNOj);)  0=229 30 

Phenyl,  Ce  Hs  =77 3° 

Phenyl  hydrate,C  nHe  0=94  32 
Phenylamine,  Ce  H  7N=93.  127 
Phlorizin,  C2iH'mOio=436.  •  •   J93 

Phlorylol,  Cs  HioO=  122 34 

Phosphines 128 

Phtalidamine,  Cg  H9  N=ii9  127 
Picrotoxin,  C5Hfl02=9*^--   '^ 

Pinite,  Ce  H12O5  =  164 in 

Piperidine,  Cr,  HiiN=8.s..i30,  141 
Piperine,  CnHigNOs  =285..  .141 

Pitch,  Burgundy 42 

Potassium,  formiate 88 

Propane,  C3  Hs  =44  ■  •  •  '3.  'S.  23 

Propenyl,  C3  H5  =41   15 

Propine,  C3  H4  =40 13 

Propone,  C3H2  =38 >3 

Propyl i.S 

Propyl  hydride,  C3  Ha  =44.  23 
Propylamine,  C3  H9  N = 59  •  •  '27 

Propylene,  C3  He  =42 22 

Proplene  iodide,C8H5  I  — 168  64 

Ptyalin 212 

Pyrethrin 42 


230 


INDEX, 


PAGE. 

Pyrolignite io6 

Pyroxylin 207 

Quercite,  Ce  HigOa  =  164. . .  181 
Quercitrin,  C!sH3oCn=65o. .  193 
Quinia,  (quinine) 

CfflHaiNa  Oa  =324 — 151, 129 
Quinicia,  G»Ha4NaOa  ..154,  129 
Quinidia,  CaoIIiiNa  Oj  =324.  129 

Quinidia,  oxalate  of 155 

Quinoidine 158 

Quinoleine,  (Quinoline), 

130.  153.157 

Quinovin,  C80H48C8  =536...  193 

Radicles,  defined 14 

Radicles,  organometallic 78 

Radicles,  organotnetalloid. . .     81 

Reagent,  Fehling's 187 

Reagent,  Haines' 187 

Reagent,  Trommer's 186 

Resins 25,  41 

Retinasphalt 25 

Retinite 25 

Rhigolene 24 

Rice 216 

Rochelle  salt, 

KNaC4H4  06  4-4aq....  118 
Rosaniline,  CaoHaiNs  6=319  31 

Rutylene,  CioH]8=  138 20 

Rye 216 

Saccharide 186 

Saccharoses,Ci2H230ti  =  .  189,182 

Salicin,  CisHisOt  =286 194 

Saligenin,  C^  Hg  Oj  =  124.. .  194 

Saponification 176 

Saponine 193 

Sinapoline,  C7  HijNa  0=  140    58 


PAGE. 

Sinnatnine,  C.|  Hg  Na  =82. .     58 

Soaps 176 

Sodium  ethyl,  Ca  H5  Na=  52  80 
Sodium  sulphocarbolate, 

NaC6H6S04=i97 33 

Solanidia,  (so'.anidine) i6j 

Solania,  (solanine) 

C43HtiNOi6=8s7..  .  165,129,193 

Sorbin,  Ce  HiaOe  =  i8o 182 

Spermaceti,  CajHeiOa  =480    179 

Spirit  of  Mindererus 105 

Stannethyl 79 

Stannethyl  iodide 79 

Starch 210 

Stearin,  (stearine) 

CstHho  Oe  =890 174 

Stearine  candles 1 76 

Stibines 128 

Stibyl 119 

Strychia,  (strychnine), 

CaiHaaNa  Oa  =334. . .  159,  129 

Styrol,C8H8=i04 38 

Sucrates 190 

Sugars 181 

Sugar  of  milk,  Ci3Hi40i2i9'.'82 
Tannin,  Ca7H2aOn=6i8..i96, 193 
Tartar  emetic, 

KSbC4  H4  O7  =325 "8 

Tetrachloropropyl, 

CsH3Cl4=i8i IS 

Tetradecane,  Ci4H3o=  198. . .  24 

Tetradecyl  hydride,  C14H30. .  24 

Tetradecylene,  Ci4H28=  >9f>-  22 
Tetrethylammonium, 

N(Ca'H5)4=i3o 133 

ThebeiajCigHaiNOs 148,  120 


L 


29.193 

.    l82 

J  179 
.   105 

•  79 

•  79 
.  210 

•  174 
.  176 
..  128 
.  119 


INDEX. 


231 


Theia,  (theine) 

Cg  H10N4  Os  =  194-  •  •  -168,  130 
Theobromine, 

C7H8N4  02=i8o....i69,  130 

Thymol,  CioH  140=  I  so 34 

Thiosinnamine, 

C4H8N2S=ii6 58 

Tobacco 140 

Toluene,  C7  Hg  =92 ^^ 

Toluidine,C7  H9  N  =  107..  127, 130 
Trehalose,  Ci2H220n= 342-  182 
Trichlorhydrin,  Cg  H5  CI3  . .  66 
Trichloroxypropyl, 

C3H2CIS  0=160.5 IS 

Tridecane,  U13H28- 184 27 

Triedecyl  hydride,  CisHjg. .  24 
Tridecylene,  Ci3H26=  182  .. .  22 
Triethylamine.Ce  Hi5N=  loi.  135 
Triethylarsine,  Ce  HuA.  —   128 


PAGB. 

Triethylenic,  diamine, 

CeHijOa  =112 170 

TriethyUtibine,  CeHwSb...  128 
Trimethylainine,  C3H9N...  128 
Trimethylphosphine.Cs  H9  P  128 
Tunicine,  (Ce  HiqOj  )x,.  .  184,  209 

Turpentine,  CioHi6=  136 35 

Types,  organic 10 

Wax 179 

Whiskey S* 

Wines 3* 

Wood-spirit 49 

Xylene,  C8Hio=  106. 28 

Xylidine,  C8HiiN=i2i 127 

Xylyl  alcohol,  CsHioOs  122.  46 
Zinc,  ethyl, 

(C2H5)2Zn= 213.2  79 

Zinc,  glycol, 

Zn(C8  H4  NO2  )i  =2i3.2...79, 126 


9.  "9 

•  38 
.  190 
.  181 
91,182 
16,193 

.  118 

••  IS 
,.  24 
,.     24 

>.       23 


■•    133 

\S,  120 


*^ 


f 


y 


